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“Mixed-valent, heteroleptic homometallic diketonates as templates for the design of volatile heterometallic precursors”. Lieberman CM, Filatov AS, Wei Z, Rogachev AY, Abakumov AM, Dikarev EV, Chemical science 6, 2835 (2015). http://doi.org/10.1039/c4sc04002c
Abstract: A novel series of mixed-valent, heteroleptic transition metal diketonates that can be utilized as prospective single-source precursors for the low-temperature preparation of oxide materials are reported. The first mixed-valent iron beta-diketonates with different Fe-III/Fe-II ratios have been synthesized by applying the mixed-ligand approach. Based on nearly quantitative reaction yields and analysis of iron-oxygen bonds, these compounds were formulated as [Fe-III(acac)(3)][Fe-II(hfac)(2)] (1) and [Fe-II(hfac)(2)][Fe-III(acac)(3)][Fe-II(hfac)(2)] (2). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated Fe-II centers chelated by two hfac (hexafluoroacetylacetonate) ligands with electron-withdrawing substituents maintain bridging interactions with oxygen atoms of electron-donating acac (acetylacetonate) groups that chelate the neighboring Fe-III atoms. Switching the ligands on Fe-III and Fe-II atoms in starting reagents resulted in the instant ligand exchange between iron centers and in yet another polynuclear homometallic diketonate [Fe-II(hfac)(2)][Fe-III(acac)(2)(hfac)][Fe-II(hfac)(2)] (3) that adheres to the same bonding pattern as in complexes 1 and 2. The proposed synthetic methodology has been extended to design heterometallic diketonates with different M : M' ratios. Homometallic parent molecules have been used as templates to obtain heterometallic mixed-valent [Fe-III(acac)(3)][Mn-II(hfac)(2)] (4) and [Ni-II(hfac)(2)] – [Fe-III(acac)(3)][Ni-II(hfac)(2)] (5) complexes. The combination of two different diketonate ligands with electron-donating and electron-withdrawing substituents was found to be crucial for maintaining the above mixed-valent heterometallic assemblies. Theoretical investigation of two possible “isomers”, [Fe-III(acac)(3)][Mn-II(hfac)(2)] (4) and [Mn-III(acac)(3)][Fe-II(hfac)(2)] (40) provided an additional support for the metal site assignment giving a preference of 9.78 kcal mol(-1) for the molecule 4. Heterometallic complexes obtained in the course of this study have been found to act as effective single-source precursors for the synthesis of mixed-transition metal oxide materials MxM2-xO3 and MxMi-xO. The title highly volatile precursors can be used for the low-temperature preparation of both amorphous and crystalline heterometallic oxides in the form of thin films or nanosized particles that are known to operate as efficient catalysts in oxygen evolution reaction.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 8.668
Times cited: 13
DOI: 10.1039/c4sc04002c
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“Molybdenum oxide nitrides of the Mo2(O,N,\square)5 type : on the way to Mo2O5”. Weber D, Huber M, Gorelik TE, Abakumov AM, Becker N, Niehaus O, Schwickert C, Culver SP, Boysen H, Senyshyn A, Poettgen R, Dronskowski R, Ressler T, Kolb U, Lerch M, Inorganic chemistry 56, 8782 (2017). http://doi.org/10.1021/ACS.INORGCHEM.7B00551
Abstract: Blue-colored molybdenum oxide nitrides of the Mo-2(O,N,square)(5) type were synthesized by direct nitridation of commercially available molybdenum trioxide with a mixture of gaseous ammonia and oxygen. Chemical composition, crystal structure, and stability of the obtained and hitherto unknown compounds are studied extensively. The average oxidation state of +5 for molybdenum is proven by Mo K near-edge X-ray absorption spectroscopy; the magnetic behavior is in agreement with compounds exhibiting (MoO6)-O-v units. The new materials are stable up to similar to 773 K in an inert gas atmosphere. At higher temperatures, decomposition is observed. X-ray and neutron powder diffraction, electron diffraction, and high-resolution transmission electron microscopy reveal the structure to be related to VNb9O24.9-type phases, however, with severe disorder hampering full structure determination. Still, the results demonstrate the possibility of a future synthesis of the potential binary oxide Mo2O5. On the basis of these findings, a tentative suggestion on the crystal structure of the potential compound Mo2O5, backed by electronic-structure and phonon calculations from first principles, is given.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 3
DOI: 10.1021/ACS.INORGCHEM.7B00551
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“Multiple twinning as a structure directing mechanism in layered rock-salt-type oxides : NaMnO2 polymorphism, redox potentials, and magnetism”. Abakumov AM, Tsirlin AA, Bakaimi I, Van Tendeloo G, Lappas A, Chemistry of materials 26, 3306 (2014). http://doi.org/10.1021/cm5011696
Abstract: New polymorphs of NaMnO2 have been observed using transmission electron microscopy and synchrotron X-ray powder diffraction. Coherent twin planes confined to the (NaMnO2) layers, parallel to the (10 (1) over bar) crystallographic planes of the monoclinic layered rock-salt-type alpha-NaMnO2 (O3) structure, form quasi-periodic modulated sequences, with the known alpha-and beta-NaMnO2 polymorphs as the two limiting cases. The energy difference between the polymorphic forms, estimated using a DFT-based structure relaxation, is on the scale of the typical thermal energies that results in a high degree of stacking disorder in these compounds. The results unveil the remarkable effect of the twin planes on both the magnetic and electrochemical properties. The polymorphism drives the magnetic ground state from a quasi-1D spin system for the geometrically frustrated alpha-polymorph through a two-leg spin ladder for the intermediate stacking sequence toward a quasi-2D magnet for the beta-polymorph. A substantial increase of the equilibrium potential for Na deintercalation upon increasing the concentration of the twin planes is calculated, providing a possibility to tune the electrochemical potential of the layered rock-salt ABO(2) cathodes by engineering the materials with a controlled concentration of twins.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 35
DOI: 10.1021/cm5011696
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“Nanoscale Characterization of Growth of Secondary Phases in Off-Stoichiometric CZTS Thin Films”. Vishwakarma M, Karakulina OM, Abakumov AM, Hadermann J, Mehta BR, Journal of nanoscience and nanotechnology 18, 1688 (2018). http://doi.org/10.1166/jnn.2018.14261
Abstract: The presence of secondary phases is one of the main issues that hinder the growth of pure kesterite Cu2ZnSnS4 (CZTS) based thin films with suitable electronic and junction properties for efficient solar cell devices. In this work, CZTS thin films with varied Zn and Sn content have been prepared by RF-power controlled co-sputtering deposition using Cu, ZnS and SnS targets and a subsequent sulphurization step. Detailed TEM investigations show that the film shows a layered structure with the majority of the top layer being the kesterite phase. Depending on the initial thin film composition, either about ~1 μm Cu-rich and Zn-poor kesterite or stoichiometric CZTS is formed as top layer. X-ray diffraction, Raman spectroscopy and transmission electron microscopy reveal the presence of Cu2−x S, ZnS and SnO2 minor secondary phases in the form of nanoinclusions or nanoparticles or intermediate layers.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 1.483
DOI: 10.1166/jnn.2018.14261
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Erni R, Abakumov AM, Rossell MD, Batuk D, Tsirlin AA, Né,nert G, Van Tendeloo G (2014) Nanoscale phase separation in perovskites revisited. London, 216–217
Keywords: L1 Letter to the editor; Electron microscopy for materials research (EMAT)
Impact Factor: 39.737
Times cited: 5
DOI: 10.1038/nmat3865
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“Nanostructures in LuFe2O4+\delta”. Hervieu M, Damay F, Poienar M, Elkaim E, Rouquette J, Abakumov AM, Van Tendeloo G, Maignan A, Martin C, Solid state sciences 23, 26 (2013). http://doi.org/10.1016/j.solidstatesciences.2013.05.015
Abstract: A LuFe2O4+delta sample, previously characterized by X-ray synchrotron and neutron diffraction, has been studied by electron microscopy techniques, in order to get a precise description of its micro- and nanostructures at room temperature. The X-ray synchrotron data vs. temperature show that the monoclinic distortion is associated with the charge ordering; this distortion results in elongated twinning domains, which enhance the complexity of the microstructural state at room temperature. The structural modulation associated with oxygen excess is observed in large domains inside a non modulated matrix, in contrast with the modulations associated with the charge ordering of the Fe2+ and Fe3+ species, which are mostly short-range. The investigation of the nature and density of defects in the sample shows that they are nano-scaled, preserving the regularity of the layer stacking mode, and limited to the formation of one- or two-units large stacking faults, associated with gliding mechanisms. Based on these observations, an original description of the LuFe2O4 ferrite structure, through puckered [LuO4](infinity) sandwiching [Fe-2](infinity) layers, is proposed. (C) 2013 Elsevier Masson SAS. All rights reserved.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 1.811
Times cited: 7
DOI: 10.1016/j.solidstatesciences.2013.05.015
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“New anion-conducting solid solutions Bi1-xTex(O,F)2+\delta (x >, 0.5) and glassceramic material on their base”. Prituzhalov VA, Ardashnikova EI, Vinogradov AA, Dolgikh VA, Videau J-J, Fargin E, Abakumov AM, Tarakina NV, Van Tendeloo G, Journal of fluorine chemistry 132, 1110 (2011). http://doi.org/10.1016/j.jfluchem.2011.06.042
Abstract: The anion-excess fluorite-like solid solutions with general composition Bi1−xTex(O,F)2+δ (x > 0.5) have been synthesized by a solid state reaction of TeO2, BiF3 and Bi2O3 at 873 K with following quenching. The homogeneity areas and polymorphism of the I ↔ IV Bi1−xTex(O,F)2+δ phases were investigated. The crystal structure of the low temperature IV-Bi1−xTex(O,F)2+δ phase has been solved using electron diffraction and X-ray powder diffraction (a = 11.53051(9) Å, S.G. Ia-3, RI = 0.046, RP = 0.041). Glass formation area in the Bi2O3BiF3TeO2 (10% TiO2) system was investigated. IVBi1−xTex(O,F)2+δ phase starts to crystallize at short-time (0.53 h) annealing of oxyfluoride glasses at temperatures above Tg (600615 K). The ionic conductivity of the crystalline Bi1−xTex(O,F)2+δ phase and corresponding glass-ceramics was investigated. Activation energy of conductivity Ea = 0.41(2) eV for the IV-Bi1−xTex(O,F)2+δ crystalline samples and Ea = 0.73 eV for the glass-ceramic samples were obtained. Investigation of the oxyfluoride samples with a constant cation ratio demonstrates essential influence of excess fluorine anions on the ionic conductivity.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.101
Times cited: 2
DOI: 10.1016/j.jfluchem.2011.06.042
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“New class of single-source precursors for the synthesis of main group-transition metal oxides: heterobimetallic Pb-Mn \beta-diketonates”. Zhang H, Yang J-H, Shpanchenko RV, Abakumov AM, Hadermann J, Clérac R, Dikarev EV, Inorganic chemistry 48, 8480 (2009). http://doi.org/10.1021/ic901107s
Abstract: Heterometallic lead−manganese â-diketonates have been isolated in pure form by several synthetic methods that include solid-state and solution techniques. Two compounds with different Pb/Mn ratios, PbMn2(hfac)6 (1) and PbMn(hfac)4 (2) (hfac = hexafluoroacetylacetonate), can be obtained in quantitative yield by using different starting materials. Single crystal X-ray investigation revealed that the solid-state structure of 1 contains trinuclear molecules in which lead metal center is sandwiched between two [Mn(hfac)3] units, while 2 consists of infinite chains of alternating [Pb(hfac)2] and [Mn(hfac)2] fragments. The heterometallic structures are held together by strong Lewis acid−base interactions between metal atoms and diketonate ligands acting in chelating-bridging fashion. Spectroscopic investigation confirmed the retention of heterometallic structures in solutions of non-coordinating solvents as well as upon sublimation-deposition procedure. Thermal decomposition of heterometallic diketonates has been systematically investigated in a wide range of temperatures and annealing times. For the first time, it has been shown that thermal decomposition of heterometallic diketonates results in mixed-metal oxides, while both the structure of precursors and the thermolysis conditions have a significant influence on the nature of the resulting oxides. Five different Pb−Mn oxides have been detected by X-ray powder diffraction when studying the decomposition of 1 and 2 in the temperature range 500−800 °C. The phase that has been previously reported as Pb0.43MnO2.18 was synthesized in the pure form by decomposition of 1, and crystallographically characterized. The orthorhombic unit cell parameters of this oxide, obtained by electron diffraction technique, have been subsequently refined using X-ray powder diffraction data. Besides that, a previously unknown lead−manganese oxide has been obtained at low temperature decomposition and short annealing times. The parameters of its monoclinically distorted unit cell have been determined. The EDX analysis revealed that this compound has a Pb/Mn ratio close to 1:4 and contains no appreciable amount of fluorine.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 28
DOI: 10.1021/ic901107s
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“New perovskite-based manganite Pb2Mn2O5”. Hadermann J, Abakumov AM, Perkisas T, d' Hondt H, Tan H, Verbeeck J, Filonenko VP, Antipov EV, Van Tendeloo G, Journal of solid state chemistry 183, 2190 (2010). http://doi.org/10.1016/j.jssc.2010.07.032
Abstract: A new perovskite based compound Pb2Mn2O5 has been synthesized using a high pressure high temperature technique. The structure model of Pb2Mn2O5 is proposed based on electron diffraction, high angle annular dark field scanning transmission electron microscopy and high resolution transmission electron microscopy. The compound crystallizes in an orthorhombic unit cell with parameters a=5.736(1)Å≈√2a p p p (a p the parameter of the perovskite subcell) and space group Pnma. The Pb2Mn2O5 structure consists of quasi two-dimensional perovskite blocks separated by 1/2[110] p (1̄01) p crystallographic shear planes. The blocks are connected to each other by chains of edge-sharing MnO5 distorted tetragonal pyramids. The chains of MnO5 pyramids and the MnO6 octahedra of the perovskite blocks delimit six-sided tunnels accommodating double chains of Pb atoms. The tunnels and pyramidal chains adopt two mirror-related configurations (left L and right R) and layers consisting of chains and tunnels of the same configuration alternate in the structure according to an -LRLR-sequence. The sequence is sometimes locally violated by the appearance of -LL- or -RR-fragments. A scheme is proposed with a JahnTeller distortion of the MnO6 octahedra with two long and two short bonds lying in the ac plane, along two perpendicular orientations within this plane, forming a d-type pattern.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 8
DOI: 10.1016/j.jssc.2010.07.032
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“Optical and photoelectrical properties of nanocrystalline indium oxide with small grains”. Forsh EA, Abakumov AM, Zaytsev VB, Konstantinova EA, Forsh PA, Rumyantseva MN, Gaskov AM, Kashkarov PK, Thin solid films : an international journal on the science and technology of thin and thick films 595, 25 (2015). http://doi.org/10.1016/j.tsf.2015.10.053
Abstract: Optical properties, spectral dependence of photoconductivity and photoconductivity decay in nanocrystalline indium oxide In2O3 are studied. A number of nanostructured In2O3 samples with various nanocrystals size are prepared by sol-gel method and characterized using various techniques. The mean nanocrystals size varies from 7 to 8 nm to 39-41 nm depending on the preparation conditions. Structural characterization of the In2O3 samples is performed by means of transmission electron microscopy and X-ray powder diffraction. The combined analysis of ultraviolet-visible absorption spectroscopy and diffuse reflectance spectroscopy shows that nanostructuring leads to the change in optical band gap: optical band gap of the In2O3 samples (with an average nanocrystal size from 7 to 41 nm) is equal to 2.8 eV. We find out the correlation between spectral dependence of photoconductivity and optical properties of nanocrystalline In2O3: sharp increase in photoconductivity was observed to begin at 2.8 eV that is equal to the optical bandgap in the In2O3 samples, and reached its maximum at 3.2-3.3 eV. The combined analysis of the slow photoconductivity decay in air, vacuum and argon, that was accurately fitted by a stretched-exponential function, and electron paramagnetic resonance (EPR) measurements shows that the kinetics of photoconductivity decay is strongly depended on the presence of oxygen molecules in the ambient of In2O3 nanocrystals. There is the quantitative correlation between EPR and photoconductivity data. Based on the obtained data we propose the model clearing up the phenomenon of permanent photoconductivity decay in nanocrystalline In2O3. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 1.879
Times cited: 18
DOI: 10.1016/j.tsf.2015.10.053
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“Ordering of tetrahedral chains in the Sr2MnGaO5 brownmillerite”. Abakumov AM, Alekseeva AM, Rozova MG, Antipov EV, Lebedev OI, Van Tendeloo G, Journal of solid state chemistry 174, 319 (2003). http://doi.org/10.1016/S0022-4596(03)00226-3
Abstract: Tetrahedral chain ordering in the Sr2MnGaO5 structure is studied using electron diffraction (ED) and high-resolution electron microscopy. The ED patterns show the presence of satellite reflections, which indicate a commensurately modulated structure with a = 5.4056(8) Angstrom b 16.171(3) Angstrom, c = 5.5592(7) Angstrom, q – 1/2c*, superspace group Immma(00gamma,)s00. The Superstructure arises due to ordering of the two types of symmetry related tetrahedral chains (L and R) according to a ... LRLR ... sequence, where L and R chains alternate along the c-axis within the same (GaO) layer. Numerous defects at different structural levels were observed, comprising interleaving L and R chains, violation of the ... LRLR ... chain sequence within one layer, different stacking modes of the ... LRLR ... ordered layers with subsequent alternation of blocks of different width along the h-axis of the brownmillerite subcell and island fragmentation of the modulated superstructure. By in situ heating ED experiments it is found that the long-range ordering of the tetrahedral chains is stable tip to 665degreesC and is completely suppressed at 905degreesC. (C) 2003 Elsevier Inc. All rights reserved.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 34
DOI: 10.1016/S0022-4596(03)00226-3
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“Origin of voltage decay in high-capacity layered oxide electrodes”. Sathiya M, Abakumov AM, Foix D, Rousse G, Ramesha K, Saubanère M, Doublet M , Vezin H, Laisa CP, Prakash AS, Gonbeau D, Van Tendeloo G, Tarascon JM, Nature materials 14, 230 (2015). http://doi.org/10.1038/nmat4137
Abstract: Although Li-rich layered oxides (Li1+xNiyCozMn1−x−y−zO2 > 250 mAh g−1) are attractive electrode materials providing energy densities more than 15% higher than todays commercial Li-ion cells, they suffer from voltage decay on cycling. To elucidate the origin of this phenomenon, we employ chemical substitution in structurally related Li2RuO3 compounds. Li-rich layered Li2Ru1−yTiyO3 phases with capacities of ~240 mAh g−1 exhibit the characteristic voltage decay on cycling. A combination of transmission electron microscopy and X-ray photoelectron spectroscopy studies reveals that the migration of cations between metal layers and Li layers is an intrinsic feature of the chargedischarge process that increases the trapping of metal ions in interstitial tetrahedral sites. A correlation between these trapped ions and the voltage decay is established by expanding the study to both Li2Ru1−ySnyO3 and Li2RuO3; the slowest decay occurs for the cations with the largest ionic radii. This effect is robust, and the finding provides insights into new chemistry to be explored for developing high-capacity layered electrodes that evade voltage decay.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 39.737
Times cited: 395
DOI: 10.1038/nmat4137
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“Original close-packed structure and magnetic properties of the Pb4Mn9O20 manganite”. Abakumov AM, Hadermann J, Tsirlin AA, Tan H, Verbeeck J, Zhang H, Dikarev EV, Shpanchenko RV, Antipov EV, Journal of solid state chemistry 182, 2231 (2009). http://doi.org/10.1016/j.jssc.2009.06.003
Abstract: The crystal structure of the Pb4Mn9O20 compound (previously known as Pb0.43MnO2.18) was solved from powder X-ray diffraction, electron diffraction, and high resolution electron microscopy data (S.G. Pnma, a=13.8888(2) Å, b=11.2665(2) Å, c=9.9867(1) Å, RI=0.016, RP=0.047). The structure is based on a 6H (cch)2 close packing of pure oxygen h-type (O16) layers alternating with mixed c-type (Pb4O12) layers. The Mn atoms occupy octahedral interstices formed by the oxygen atoms of the close-packed layers. The MnO6 octahedra share edges within the layers, whereas the octahedra in neighboring layers are linked through corner sharing. The relationship with the closely related Pb3Mn7O15 structure is discussed. Magnetization measurements reveal a peculiar magnetic behavior with a phase transition at 52 K, a small net magnetization below the transition temperature, and a tendency towards spin freezing.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 5
DOI: 10.1016/j.jssc.2009.06.003
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“Oxidation potential in the Earth's lower mantle as recorded by ferropericlase inclusions in diamond”. Kaminsky FV, Ryabchikov ID, McCammon CA, Longo M, Abakumov AM, Turner S, Heidari H, Earth and planetary science letters 417, 49 (2015). http://doi.org/10.1016/j.epsl.2015.02.029
Abstract: Ferropericlase (fPer) inclusions from kimberlitic lower-mantle diamonds recovered in the Juina area, Mato Grosso State, Brazil were analyzed with transmission electron microscopy, electron energy-loss spectroscopy and the flank method. The presence of exsolved non-stoichiometric Fe3+-enriched clusters, varying in size from 1-2 nm to 10-15 nm and comprising similar to 3.64 vol.% of fPer was established. The oxidation conditions necessary for fPer formation within the uppermost lower mantle (P = 25 GPa, T = 1960 K) vary over a wide range: Delta log f(o2) (IW) from 1.58 to 7.76 (Delta = 6.2), reaching the fayalite-magnetite-quartz (FMQ) oxygen buffer position. This agrees with the identification of carbonates and free silica among inclusions within lower-mantle Juina diamonds. On the other hand, at the base of the lower mantle Delta log f(o2) values may lie at and below the iron-wustite (IW) oxygen buffer. Hence, the variations of Delta log f(o2) values within the entire sequence of the lower mantle may reach ten logarithmic units, varying from the IW buffer to the FMQ buffer values. The similarity between lower- and upper-mantle redox conditions supports whole mantle convection, as already suggested on the basis of nitrogen and carbon isotopic compositions in lower- and upper-mantle diamonds. The mechanisms responsible for redox differentiation in the lower mantle may include subduction of oxidized crustal material, mechanical separation of metallic phase(s) and silicate-oxide mineral assemblages enriched in ferric iron, as well as transfer of fused silicate-oxide material presumably also enriched in ferric iron through the mantle. (C) 2015 Elsevier B.V. All rights reserved.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.409
Times cited: 23
DOI: 10.1016/j.epsl.2015.02.029
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“Oxygen and fluorine doping in Sr2MnGaO5 brownmillerite”. Antipov EV, Abakumov AM, Alekseeva AM, Rozova MG, Hadermann J, Lebedev OI, Van Tendeloo G, Physica status solidi: A: applied research 201, 1403 (2004). http://doi.org/10.1002/pssa.200304428
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Times cited: 9
DOI: 10.1002/pssa.200304428
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“Oxygen exchange on nanocrystalline tin dioxide modified by palladium”. Frolov DD, Kotovshchikov YN, Morozov IV, Boltalin AI, Fedorova AA, Marikutsa AV, Rumyantseva MN, Gaskov AM, Sadovskaya EM, Abakumov AM, Journal of solid state chemistry 186, 1 (2012). http://doi.org/10.1016/j.jssc.2011.11.028
Abstract: Temperature-programmed oxygen isotopic exchange study was performed on nanocrystalline tin dioxide-based materials synthesized via sol-gel route and modified by palladium. Such materials are widely used as resistive gas sensors. The experiments were carried out in a flow-reactor up to complete isotopic substitution of oxygen. Substantial rates of isotopic exchange for SnO2 were observed from about 700 K. The distribution of isotopic molecules O-16(2). (OO)-O-16-O-18 and O-18(2) corresponds to simple dioxygen heteroexchange mechanism with single lattice oxygen atom. The modification of SnO2 by Pd introduced multiple heteroexchange mechanism with preliminary O-2 dissociation on the clusters surface. Spill-over of atomic oxygen from Pd to the surface of SnO2 and fast exchange with lattice oxygen result in more than 100% increase of apparent heteroexchange rate. The exchange on SnO2/Pd was shown to be a complex process involving partial deactivation of the catalytic centers at temperature higher than 750 K. (C) 2011 Elsevier Inc. All rights reserved.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 34
DOI: 10.1016/j.jssc.2011.11.028
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“Oxygen-driven competition between low-dimensional structures of Sr3CoMO6 and Sr3CoMO7-\delta with M = Ru,Ir”. Mikhailova D, Reichel P, Tsirlin AA, Abakumov AM, Senyshyn A, Mogare KM, Schmidt M, Kuo CY, Pao CW, Pi TW, Lee JF, Hu Z, Tjeng LH;, Journal of the Chemical Society : Dalton transactions 43, 13883 (2014). http://doi.org/10.1039/c4dt01893a
Abstract: We have realized a reversible structure transformation of one-dimensional 1D K4CdCl6-type Sr3CoMO6 with the Co2+/M4+ cation ordering into the two-dimensional 2D double layered Ruddlesden-Popper structure Sr3CoMO7-delta with a random distribution of Co and M (with M = Ru, Ir) upon increasing the partial oxygen pressure. The combined soft and hard X-ray absorption spectroscopy studies show that under transformation, Co and M cations were oxidized to Co3+ and M5+. During oxidation, high-spin Co2+ in Sr3CoMO6 first transforms into high-spin Co3+ in oxygen-deficient Sr3CoMO7-delta, and then further transforms into low-spin Co3+ in fully oxidized Sr3CoMO7 upon further increasing the partial pressure of oxygen. The 1D Sr3CoMO6 compound is magnetically ordered at low temperatures with the magnetic moments lying along the c-axis. Their alignment is parallel for Sr3CoRuO6 and antiparallel for Sr3CoIrO6. The 2D compounds reveal a spin-glass-like behavior related to the random distribution of magnetic cations in the structure.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.029
Times cited: 7
DOI: 10.1039/c4dt01893a
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“p -CoO x / n -SnO 2 nanostructures: New highly selective materials for H 2 S detection”. Rumyantseva MN, Vladimirova SA, Vorobyeva NA, Giebelhaus I, Mathur S, Chizhov AS, Khmelevsky NO, Aksenenko AY, Kozlovsky VF, Karakulina OM, Hadermann J, Abakumov AM, Gaskov AM, Sensors and actuators : B : chemical (2017). http://doi.org/10.1016/j.snb.2017.08.096
Abstract: Nanostructures p-CoOx/n-SnO2 based on tin oxide nanowires have been prepared by two step CVD technique and characterized in detail by XRD, XRF, XPS, HAADF-STEM imaging and EDX-STEM mapping. Depending on the temperature of decomposition of cobalt complex during the second step of CVD synthesis of nanostructures cobalt oxide forms a coating and/or isolated nanoparticles on SnO2 nanowire surface. It was found that cobalt presents in +2 and +3 oxidation states. The measurements of gas sensor properties have been carried out during exposure to CO (14 ppm), NH3 (21 ppm), and H2S (2 ppm) in dry air. The opposite trends were observed in the effect of cobalt oxide on the SnO2 gas sensitivity when detecting CO or NH3 in comparison to H2S. The decrease of sensor signal toward CO and NH3 was attributed to high catalytic activity of Co3O4 in oxidation of these gases. Contrary, the significant increase of sensor signal in the presence of H2S was attributed to the formation of metallic cobalt sulfide and removal of the barrier between p-CoOx and n-SnO2. This effect provides an excellent selectivity of p-CoOx/n-SnO2 nanostructures in H2S detection.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 5.401
Times cited: 13
DOI: 10.1016/j.snb.2017.08.096
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“Pb2.85Ba2.15Fe4SnO13 : a new member of the AnBnO3n-2 anion-deficient perovskite-based homologous series”. Korneychik OE, Batuk M, Abakumov AM, Hadermann J, Rozova MG, Sheptyakov DV, Pokholok KV, Filimonov DS, Antipov EV, Journal of solid state chemistry 184, 3150 (2011). http://doi.org/10.1016/j.jssc.2011.09.029
Abstract: Pb2.85Ba2.15Fe4SnO13, a new n=5 member of the anion-deficient perovskite based AnBnO3n−2 (A=Pb, Ba, B=Fe, Sn) homologous series, was synthesized by the solid state method. The crystal structure of Pb2.85Ba2.15Fe4SnO13 was investigated using a combination of neutron powder diffraction, electron diffraction, high angle annular dark field scanning transmission electron microscopy and Mössbauer spectroscopy. It crystallizes in the Ammm space group with unit cell parameters a=5.7990(1) Å, b=4.04293(7) Å and c=26.9561(5) Å. The Pb2.85Ba2.15Fe4SnO13 structure consists of quasi two-dimensional perovskite blocks separated by 1/2[110](1̄01)p crystallographic shear (CS) planes. The corner-sharing FeO6 octahedra at the CS planes are transformed into edge-sharing FeO5 distorted tetragonal pyramids. The octahedral positions in the perovskite blocks between the CS planes are jointly taken up by Fe and Sn, with a preference of Sn towards the position at the center of the perovskite block. The chains of FeO5 pyramids and (Fe,Sn)O6 octahedra of the perovskite blocks delimit six-sided tunnels at the CS planes occupied by double chains of Pb atoms. The compound is antiferromagnetically ordered below TN=368±15 K.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 7
DOI: 10.1016/j.jssc.2011.09.029
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“Pb2MnTeO6 double perovskite : an antipolar anti-ferromagnet”. Retuerto M, Skiadopoulou S, Li MR, Abakumov AM, Croft M, Ignatov A, Sarkar T, Abbett BM, Pokorný, J, Savinov M, Nuzhnyy D, Prokleška J, Abeykoon M, Stephens PW, Hodges JP, Vaněk P, Fennie CJ, Rabe KM, Kamba S, Greenblatt M;, Inorganic chemistry 55, 4320 (2016). http://doi.org/10.1021/acs.inorgchem.6b00054
Abstract: Pb2MnTeO6, a new double perovskite, was synthesized. Its crystal structure was determined by synchrotron X-ray and powder neutron diffraction. Pb2MnTeO6 is monoclinic (I2/m) at room temperature with a regular arrangement of all the cations in their polyhedra. However, when the temperature is lowered to similar to 120 K it undergoes a phase transition from I2/m to C2/c structure. This transition is accompanied by a displacement of the Pb atoms from the center of their polyhedra due to the 6s2 lone-pair electrons, together with a surprising off-centering of Mn2+ (d5) magnetic cations. This strong first-order phase transition is also evidenced by specific heat, dielectric, Raman, and infrared spectroscopy measurements. The magnetic characterizations indicate an anti-ferromagnetic (AFM) order below TN approximate to 20 K; analysis of powder neutron diffraction data confirms the magnetic structure with propagation vector k = (0 1 0) and collinear AFM spins. The observed jump in dielectric permittivity near similar to 150 K implies possible anti-ferroelectric behavior; however, the absence of switching suggests that Pb2MnTeO6 can only be antipolar. First-principle calculations confirmed that the crystal and magnetic structures determined are locally stable and that anti-ferroelectric switching is unlikely to be observed in Pb2MnTeO6.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 9
DOI: 10.1021/acs.inorgchem.6b00054
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“Pb5Fe3TiO11Cl : a rare example of Ti(IV) in a square pyramidal oxygen coordination”. Batuk M, Batuk D, Abakumov AM, Hadermann J, Journal of solid state chemistry 215, 245 (2014). http://doi.org/10.1016/j.jssc.2014.04.002
Abstract: A new oxychloride Pb5Fe3TiO11Cl has been synthesized using the solid state method. Its crystal and magnetic structure was investigated in the 1.5550 K temperature range using electron diffraction, high angle annular dark field scanning transmission electron microscopy, atomic resolution energy dispersive X-ray spectroscopy, neutron and X-ray powder diffraction. At room temperature Pb5Fe3TiO11Cl crystallizes in the P4/mmm space group with the unit cell parameters a=3.91803(3) Å and c=19.3345(2) Å. Pb5Fe3TiO11Cl is a new n=4 member of the oxychloride perovskite-based homologous series An+1BnO3n−1Cl. The structure is built of truncated Pb3Fe3TiO11 quadruple perovskite blocks separated by CsCl-type Pb2Cl slabs. The perovskite blocks consist of two layers of (Fe,Ti)O6 octahedra sandwiched between two layers of (Fe,Ti)O5 square pyramids. The Ti4+ cations are preferentially located in the octahedral layers, however, the presence of a noticeable amount of Ti4+ in a five-fold coordination environment has been undoubtedly proven using neutron powder diffraction and atomic resolution compositional mapping. Pb5Fe3TiO11Cl is antiferromagnetically ordered below 450(10) K. The ordered Fe magnetic moments at 1.5 K are 4.06(4) μB and 3.86(5) μB on the octahedral and square-pyramidal sites, respectively.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 4
DOI: 10.1016/j.jssc.2014.04.002
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“Pd nanoparticles on SnO2(Sb) whiskers : aggregation and reactivity in CO detection”. Zhukova AA, Rumyantseva MN, Zaytsev VB, Zaytseva AV, Abakumov AM, Gaskov AM, Journal of alloys and compounds 565, 6 (2013). http://doi.org/10.1016/j.jallcom.2013.02.184
Abstract: Single crystal antimony-doped SnO2 whiskers have been synthesized by in situ doping process in horizontal flow reactor. The produced whiskers were modified with 0.1, 0.2, 0.5, 1 or 2 wt.% Pd. The processes of Pd particles growth and aggregation are described on the base of AFM and STEM data. Depending on the content of introduced Pd precursor, the various mechanisms (Volmer-Weber or Stranski-Krastanov) of Pd nanoparticles growth realize. The dependence of sensor signal to CO on Pd concentration has non-monotonous character determined by the size of Pd nanoparticles and their aggregation degree. The best sensor signal toward CO was observed for whiskers decorated with 0.1 wt.% Pd. This concentration corresponds to the presence of individual 3-5 nm Pd nanoparticles on the surface of the whiskers. (C) 2013 Elsevier B.V. All rights reserved.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 3.133
DOI: 10.1016/j.jallcom.2013.02.184
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“Pd5InSe and Pd8In2Se : new metal-rich homological selenides with 2D palladium-indium fragments : synthesis, structure and bonding”. Zakharova EY, Kazakov SM, Isaeva AA, Abakumov AM, Van Tendeloo G, Kuznetsov AN, Journal of alloys and compounds 589, 48 (2014). http://doi.org/10.1016/j.jallcom.2013.11.172
Abstract: Two new metal-rich palladium-indium selenides, Pd5InSe and Pd8In2Se, were synthesized using a high-temperature ampoule technique. Their crystal structures were determined from Rietveld analysis of powder diffraction data, supported by energy-dispersive X-ray spectroscopy and selected area electron diffraction. Both compounds crystallize in tetragonal system with P4/mmm space group (Pd5InSe: a = 4.0290(3) angstrom, c = 6.9858(5) angstrom, Z = 1; Pd8In2Se: a = 4.0045(4) angstrom, c = 10.952(1) angstrom, Z = 1). The first compound belongs to the Pd5TlAs structure type, while the second one – to a new structure type. Main structural units in both selenides are indium-centered [Pd12In] cuboctahedra of the tetragonally distorted Cu3Au type, single-and double-stacked along the c axis in Pd5InSe and Pd8In2Se, respectively, alternating with [Pd8Se] rectangular prisms. DFT electronic structure calculations predict both compounds to be 3D metallic conductors and Pauli-like paramagnets. According to the bonding analysis based on the electron localization function topology, both compounds feature multi-centered palladium-indium interactions in their heterometallic fragments. (C) 2013 Elsevier B. V. All rights reserved.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 3.133
Times cited: 12
DOI: 10.1016/j.jallcom.2013.11.172
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“Peierls distortion, magnetism, and high hardness of manganese tetraboride”. Gou H, Tsirlin AA, Bykova E, Abakumov AM, Van Tendeloo G, Richter A, Ovsyannikov SV, Kurnosov AV, Trots DM, Konôpková, Z, Liermann HP, Dubrovinsky L, Dubrovinskaia N;, Physical review : B : condensed matter and materials physics 89, 064108 (2014). http://doi.org/10.1103/PhysRevB.89.064108
Abstract: We report crystal structure, electronic structure, and magnetism of manganese tetraboride, MnB4, synthesized under high-pressure, high-temperature conditions. In contrast to superconducting FeB4 and metallic CrB4, which are both orthorhombic, MnB4 features a monoclinic crystal structure. Its lower symmetry originates from a Peierls distortion of the Mn chains. This distortion nearly opens the gap at the Fermi level, but despite the strong dimerization and the proximity of MnB4 to the insulating state, we find indications for a sizable paramagnetic effective moment of about 1.7 mu(B)/f.u., ferromagnetic spin correlations, and, even more surprisingly, a prominent electronic contribution to the specific heat. However, no magnetic order has been observed in standard thermodynamic measurements down to 2 K. Altogether, this renders MnB4 a structurally simple but microscopically enigmatic material; we argue that its properties may be influenced by electronic correlations.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 3.836
Times cited: 39
DOI: 10.1103/PhysRevB.89.064108
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“Perovskite-like Mn2O3 : a path to new manganites”. Ovsyannikov SV, Abakumov AM, Tsirlin AA, Schnelle W, Egoavil R, Verbeeck J, Van Tendeloo G, Glazyrin KV, Hanfland M, Dubrovinsky L, Angewandte Chemie 52, 1494 (2013). http://doi.org/10.1002/anie.201208553
Abstract: Korund-artiges ε-Mn2O3 und Perowskit-artiges ζ-Mn2O3, zwei neue Phasen von Mn2O3, wurden unter hohen Drücken bei hohen Temperaturen synthetisiert. Die Manganatome können vollständig die A- und B-Positionen der Perowskitstruktur besetzen. ζ-Mn2O3 (siehe Bild, A-Positionsordnung) enthält Mn in den drei Oxidationsstufen +II, +III und +IV.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 11.994
Times cited: 84
DOI: 10.1002/anie.201208553
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“Phase separation and frustrated square lattice magnetism of Na1.5VOPO4F0.5”. Tsirlin AA, Nath R, Abakumov AM, Furukawa Y, Johnston DC, Hemmida M, Krug von Nidda H-A, Loidl A, Geibel C, Rosner H, Physical review : B : condensed matter and materials physics 84, 014429 (2011). http://doi.org/10.1103/PhysRevB.84.014429
Abstract: Crystal structure, electronic structure, and magnetic behavior of the spin-1/2 quantum magnet Na1.5VOPO4F0.5 are reported. The disorder of Na atoms leads to a sequence of structural phase transitions revealed by synchrotron x-ray powder diffraction and electron diffraction. The high-temperature second-order α↔β transition at 500 K is of the order-disorder type, whereas the low-temperature β↔γ+γ′ transition around 250 K is of the first order and leads to a phase separation toward the polymorphs with long-range (γ) and short-range (γ′) order of Na. Despite the complex structural changes, the magnetic behavior of Na1.5VOPO4F0.5 probed by magnetic susceptibility, heat capacity, and electron spin resonance measurements is well described by the regular frustrated square lattice model of the high-temperature α-polymorph. The averaged nearest-neighbor and next-nearest-neighbor couplings are J̅ 1≃−3.7 K and J̅ 2≃6.6 K, respectively. Nuclear magnetic resonance further reveals the long-range ordering at TN=2.6 K in low magnetic fields. Although the experimental data are consistent with the simplified square-lattice description, band structure calculations suggest that the ordering of Na atoms introduces a large number of inequivalent exchange couplings that split the square lattice into plaquettes. Additionally, the direct connection between the vanadium polyhedra induces an unusually strong interlayer coupling having effect on the transition entropy and the transition anomaly in the specific heat. Peculiar features of the low-temperature crystal structure and the relation to isostructural materials suggest Na1.5VOPO4F0.5 as a parent compound for the experimental study of tetramerized square lattices as well as frustrated square lattices with different values of spin.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 3.836
Times cited: 47
DOI: 10.1103/PhysRevB.84.014429
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“Phase transitions in K3AlF6”. Abakumov AM, Rossell MD, Alekseeva AM, Vassiliev SY, Mudrezova SN, Van Tendeloo G, Antipov EV, Journal of solid state chemistry 179, 421 (2006). http://doi.org/10.1016/j.jssc.2005.10.044
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 18
DOI: 10.1016/j.jssc.2005.10.044
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“Photocatalytic process optimisation for ethylene oxidation”. Tytgat T, Hauchecorne B, Abakumov AM, Smits M, Verbruggen SW, Lenaerts S, Chemical engineering journal 209, 494 (2012). http://doi.org/10.1016/j.cej.2012.08.032
Abstract: When studying photocatalysis it is important to consider, beside the chemical approach, the engineering part related to process optimisation. To achieve this a fixed bed photocatalytic set-up consisting of different catalyst placings, in order to vary catalyst distribution, is studied. The use of a fixed quantity of catalyst placed packed or randomly distributed in the reactor, results in an almost double degradation for the distributed catalyst. Applying this knowledge leads to an improved performance with limited use of catalyst. A reactor only half filled with catalyst leads to higher degradation performance compared to a completely filled reactor. Taking into account this simple process optimisation by better distributing the catalyst a more sustainable photocatalytic air purification process is achieved. (C) 2012 Elsevier B.V. All rights reserved.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT); Sustainable Energy, Air and Water Technology (DuEL)
Impact Factor: 6.216
Times cited: 12
DOI: 10.1016/j.cej.2012.08.032
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“Photoconductivity of nanocrystalline SnO2 sensitized with colloidal CdSe quantum dots”. Vasiliev RB, Babynina AV, Maslova OA, Rumyantseva MN, Ryabova LI, Dobrovolsky AA, Drozdov KA, Khokhlov DR, Abakumov AM, Gaskov AM, Journal of materials chemistry C : materials for optical and electronic devices 1, 1005 (2013). http://doi.org/10.1039/c2tc00236a
Abstract: A highly reproducible photoresponse is observed in nanocrystalline SnO2 thick films sensitized with CdSe quantum dots. The effect of the SnO2 matrix microstructure on the photoconductivity kinetics and photoresponse amplitude is demonstrated. The photoresponse of the sensitized SnO2 thick films reaches more than two orders of magnitude under illumination with the wavelength of the excitonic transition of the quantum dots. Long-term photoconductivity kinetics and photoresponse dependence on illumination intensity reveal power-law behavior inherent to the disordered nature of SnO2. The photoconductivity of the samples rises with the coarsening of the granular structure of the SnO2 matrix. At the saturation region, the photoresponse amplitude remains stable under 10(4) pulses of illumination switching, demonstrating a remarkably high stability.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 5.256
Times cited: 13
DOI: 10.1039/c2tc00236a
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“Polyoxocationic antimony oxide cluster with acidic protons”. Watanabe Y, Hyeon-Deuk K, Yamamoto T, Yabuuchi M, Karakulina OM, Noda Y, Kurihara T, Chang I-Y, Higashi M, Tomita O, Tassel C, Kato D, Xia J, Goto T, Brown CM, Shimoyama Y, Ogiwara N, Hadermann J, Abakumov AM, Uchida S, Abe R, Kageyama H, Science Advances 8, eabm5379 (2022). http://doi.org/10.1126/SCIADV.ABM5379
Abstract: The success and continued expansion of research on metal-oxo clusters owe largely to their structural richness and wide range of functions. However, while most of them known to date are negatively charged polyoxometalates, there is only a handful of cationic ones, much less functional ones. Here, we show an all-inorganic hydroxyiodide [H(10.)7Sb(32.1)O(44)][H2.1Sb2.1I8O6][Sb0.76I6](2)center dot 25H(2)O (HSbOI), forming a face-centered cubic structure with cationic Sb32O44 clusters and two types of anionic clusters in its interstitial spaces. Although it is submicrometer in size, electron diffraction tomography of HSbOI allowed the construction of the initial structural model, followed by powder Rietveld refinement to reach the final structure. The cationic cluster is characterized by the presence of acidic protons on its surface due to substantial Sb3+ deficiencies, which enables HSbOI to serve as an excellent solid acid catalyst. These results open up a frontier for the exploration and functionalization of cationic metal-oxo clusters containing heavy main group elements.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 13.6
DOI: 10.1126/SCIADV.ABM5379
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