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Author Subban, C.V.; Ati, M.; Rousse, G.; Abakumov, A.M.; Van Tendeloo, G.; Janot, R.; Tarascon, J.-M.
Title Preparation, structure, and electrochemistry of layered polyanionic hydroxysulfates : LiMSO4OH (M = Fe, Co, Mn) electrodes for Li-Ion batteries Type A1 Journal article
Year 2013 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 135 Issue 9 Pages 3653-3661
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The Li-ion rechargeable battery, due to its high energy density, has driven remarkable advances in portable electronics. Moving toward more sustainable electrodes could make this technology even more attractive to large-volume applications. We present here a new family of 3d-metal hydroxysulfates of general formula LiMSO4OH (M = Fe, Co, and Mn) among which (i) LiFeSO4OH reversibly releases 0.7 Li+ at an average potential of 3.6 V vs Li+/Li-0, slightly higher than the potential of currently lauded LiFePO4 (3.45 V) electrode material, and (ii) LiCoSO4OH shows a redox activity at 4.7 V vs Li+/Li-0. Besides, these compounds can be easily made at temperatures near 200 degrees C via a synthesis process that enlists a new intermediate phase of composition M-3(SO4)(2)(OH)(2) (M = Fe, Co, Mn, and Ni), related to the mineral caminite. Structurally, we found that LiFeSO4OH is a layered phase unlike the previously reported 3.2 V tavorite LiFeSO4OH. This work should provide an impetus to experimentalists for designing better electrolytes to fully tap the capacity of high-voltage Co-based hydroxysulfates, and to theorists for providing a means to predict the electrochemical redox activity of two polymorphs.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000315936700056 Publication Date 2013-02-01
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863;1520-5126; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 53 Open Access
Notes Approved Most recent IF: 13.858; 2013 IF: 11.444
Call Number UA @ lucian @ c:irua:108283 Serial 2708
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Author Schröder, F.; Esken, D.; Cokoja, M.; van den Berg, M.W.E.; Lebedev, O.I.; Van Tendeloo, G.; Walaszek, B.; Buntkowsky, G.; Limbach, H.H.; Chaudret, B.; Fischer, R.A.;
Title Ruthenium nanoparticles inside porous (Zn40(bdC)(3)) by hydrogenolysis of adsorbed (Ru(cod)(cot)): a solid-state reference system for surfactant-stabilized ruthenium colloids Type A1 Journal article
Year 2008 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 130 Issue 19 Pages 6119-6130
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000255620200018 Publication Date 2008-04-11
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863;1520-5126; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 272 Open Access
Notes Esteem 026019 Approved Most recent IF: 13.858; 2008 IF: 8.091
Call Number UA @ lucian @ c:irua:68851 Serial 2934
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Author Quintana, M.; Grzelczak, M.; Spyrou, K.; Calvaresi, M.; Bals, S.; Kooi, B.; Van Tendeloo, G.; Rudolf, P.; Zerbetto, F.; Prato, M.
Title A simple road for the transformation of few-layer graphene into MWNTs Type A1 Journal article
Year 2012 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 134 Issue 32 Pages 13310-13315
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract We report the direct formation of multiwalled carbon nanotubes (MWNT) by ultrasonication of graphite in dimethylformamide (DMF) upon addition of ferrocene aldehyde (Fc-CHO). The tubular structures appear exclusively at the edges of graphene layers and contain Fe clusters. Pc in conjunction with benzyl aldehyde, or other Fc derivatives, does not induce formation of NT. Higher amounts of Fc-CHO added to the dispersion do not increase significantly MWNT formation. Increasing the temperature reduces the amount of formation of MWNTs and shows the key role of ultrasound-induced cavitation energy. It is concluded that Fc-CHO first reduces the concentration of radical reactive species that slice graphene into small moieties, localizes itself at the edges of graphene, templates the rolling up of a sheet to form a nanoscroll, where it remains trapped, and finally accepts and donates unpaired electron to the graphene edges and converts the less stable scroll into a MWNT. This new methodology matches the long held notion that CNTs are rolled up graphene layers. The proposed mechanism is general and will lead to control the production of carbon nanostructures by simple ultrasonication treatments.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000307487200034 Publication Date 2012-05-08
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863;1520-5126; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 56 Open Access
Notes This work was supported by the University of Trieste, the Italian Ministry of Education MIUR (cofin Prot. 20085M27SS), the European Union through the ERC grant No. 246791 – COUNTATOMS, the grant agreement for an Integrated Infrastructure Initiative N. 262348 ESMI, and the “Graphene-based electronics” research program of the Foundation for Fundamental Research on Matter (FOM). Approved Most recent IF: 13.858; 2012 IF: 10.677
Call Number UA @ lucian @ c:irua:101109 Serial 3003
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Author Kneller, J.M.; Soto, R.J.; Surber, S.E.; Colomer, J.F.; Fonseca, A.; Nagy, J.B.; Van Tendeloo, G.; Pietrass, T.
Title TEM and laser-polarized 129Xe NMR characterization of oxidatively purified carbon nanotubes Type A1 Journal article
Year 2000 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 122 Issue 43 Pages 10591-10597
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract Multiwall carbon nanotubes are produced by decomposition of acetylene at 600 degreesC on metal catalysts supported on NaY zeolite. The support and the metal are eliminated by dissolving them in aqueous hydrofluoric acid (HF). Two methods were used to eliminate the pyrolitic carbon: oxidation in air at 500 degreesC and oxidation by potassium permanganate in acidic solution at 70 degreesC. The progress and efficacy of the purification methods are verified by TEM. The properties of the purified multiwalled carbon nanotubes are probed using C-13 and Xe-129 NMR spectroscopy under continuous-flow optical-pumping conditions. Xenon is shown to penetrate the interior of the nanotubes. A distribution of inner tube diameters gives rise to chemical shift dispersion. When the temperature is lowered, an increasing fraction of xenon resides inside the nanotubes and is not capable of exchanging with xenon in the interparticle space. In the case of the permanganate-oxidized sample, rapid xenon relaxation is attributed to interaction with residual MnO2 nanoparticles in the interior of the tubes.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000165205000011 Publication Date 2002-07-26
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863;1520-5126; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 53 Open Access
Notes Approved Most recent IF: 13.858; 2000 IF: 6.025
Call Number UA @ lucian @ c:irua:95741 Serial 3473
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Author Hadermann, J.; Abakumov, A.M.; Adkin, J.J.; Hayward, M.A.
Title Topotactic reduction as a route to new close-packed anion deficient perovskites: structure and magnetism of 4H-BaMnO2+x Type A1 Journal article
Year 2009 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 131 Issue 30 Pages 10598-10604
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The anion-deficient perovskite 4H-BaMnO2+x has been obtained by a topotactic reduction, with LiH, of the hexagonal perovskite 4H-BaMnO3−x. The crystal structure of 4H-BaMnO2+x was solved using electron diffraction and X-ray powder diffraction and further refined using neutron powder diffraction (S.G. Pnma, a = 10.375(2) Å, b = 9.466(2) Å, c = 11.276(3) Å, at 373 K). The orthorhombic superstructure arises from the ordering of oxygen vacancies within a 4H (chch) stacking of close packed c-type BaO2.5 and h-type BaO1.5 layers. The ordering of the oxygen vacancies transforms the Mn2O9 units of face-sharing MnO6 octahedra into Mn2O7 (two corner-sharing tetrahedra) and Mn2O6 (two edge-sharing tetrahedra) groups. The Mn2O7 and Mn2O6 groups are linked by corner-sharing into a three-dimensional framework. The structures of the BaO2.5 and BaO1.5 layers are different from those observed previously in anion-deficient perovskites providing a new type of order pattern of oxygen atoms and vacancies in close packed structures. Magnetization measurements and neutron diffraction data reveal 4H-BaMnO2+x adopts an antiferromagnetically ordered state below TN ≈ 350 K.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000268644400056 Publication Date 2009-07-01
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863;1520-5126; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 25 Open Access
Notes Approved Most recent IF: 13.858; 2009 IF: 8.580
Call Number UA @ lucian @ c:irua:77928 Serial 3681
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Author Ati, M.; Sathiya, M.; Boulineau, S.; Reynaud, M.; Abakumov, A.; Rousse, G.; Melot, B.; Van Tendeloo, G.; Tarascon, J.-M.
Title Understanding and promoting the rapid preparation of the triplite-phase of LiFeSO4F for use as a large-potential Fe cathode Type A1 Journal article
Year 2012 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 134 Issue 44 Pages 18380-18387
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The development of new electrode materials, which are composed of Earth-abundant elements and that can be made via eco-efficient processes, is becoming absolutely necessary for reasons of sustainable production. The 3.9 V triplite-phase of LiFeSO4F, compared to the 3.6 V tavorite-phase, could satisfy this requirement provided the currently complex synthetic pathway can be simplified. Here, we present our work aiming at better understanding the reaction mechanism that govern its formation as a way to optimize its preparation. We first demonstrate, using complementary X-ray diffraction and transmission electron microscopy studies, that triplite-LiFeSO4F can nucleate from tavorite-LiFeSO4F via a reconstructive process whose kinetics are significantly influenced by moisture and particle morphology. Perhaps the most spectacular finding is that it is possible to prepare electrochemically active triplite-LiFeSO4F from anhydrous precursors using either reactive spark plasma sintering (SPS) synthesis in a mere 20 min at 320 degrees C or room temperature ball milling for 3 h. These new pathways appear to be strongly driven by the easy formation of a disordered phase with higher entropy, as both techniques trigger disorder via rapid annealing steps or defect creation. Although a huge number of phases adopts the tavorite structure-type, this new finding offers both a potential way to prepare new compositions in the triplite structure and a wealth of opportunities for the synthesis of new materials which could benefit many domains beyond energy storage.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000310720900041 Publication Date 2012-10-12
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863;1520-5126; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 36 Open Access
Notes Approved Most recent IF: 13.858; 2012 IF: 10.677
Call Number UA @ lucian @ c:irua:105147 Serial 3802
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Author McCalla, E.; Sougrati, M.T.; Rousse, G.; Berg, E.J.; Abakumov, A.; Recham, N.; Ramesha, K.; Sathiya, M.; Dominko, R.; Van Tendeloo, G.; Novák, P.; Tarascon, J.M.;
Title Understanding the roles of anionic redox and oxygen release during electrochemical cycling of lithium-rich layered Li4FeSbO6 Type A1 Journal article
Year 2015 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 137 Issue 137 Pages 4804-4814
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract Li-rich oxides continue to be of immense interest as potential next generation Li-ion battery positive electrodes, and yet the role of oxygen during cycling is still poorly understood. Here, the complex electrochemical behavior of Li4FeSbO6 materials is studied thoroughly with a variety of methods. Herein, we show that oxygen release occurs at a distinct voltage plateau from the peroxo/superoxo formation making this material ideal for revealing new aspects of oxygen redox processes in Li-rich oxides. Moreover, we directly demonstrate the limited reversibility of the oxygenated species (O-2(n-); n = 1, 2, 3) for the first time. We also find that during charge to 4.2 V iron is oxidized from +3 to an unusual +4 state with the concomitant formation of oxygenated species. Upon further charge to 5.0 V, an oxygen release process associated with the reduction of iron +4 to +3 is present, indicative of the reductive coupling mechanism between oxygen and metals previously reported. Thus, in full state of charge, lithium removal is fully compensated by oxygen only, as the iron and antimony are both very close to their pristine states. Besides, this charging step results in complex phase transformations that are ultimately destructive to the crystallinity of the material. Such findings again demonstrate the vital importance of fully understanding the behavior of oxygen in such systems. The consequences of these new aspects of the electrochemical behavior of lithium-rich oxides are discussed in detail.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000353177100036 Publication Date 2015-03-26
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863;1520-5126; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 86 Open Access
Notes Approved Most recent IF: 13.858; 2015 IF: 12.113
Call Number c:irua:126019 Serial 3805
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Author Yang, Z.; Altantzis, T.; Zanaga, D.; Bals, S.; Van Tendeloo, G.; Pileni, M.-P.
Title Supracrystalline Colloidal Eggs: Epitaxial Growth and Freestanding Three-Dimensional Supracrystals in Nanoscaled Colloidosomes Type A1 Journal article
Year 2016 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 138 Issue 138 Pages 3493-3500
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The concept of template-confined chemical reactions allows the synthesis of complex molecules that would hardly be producible through conventional method. This idea was developed to produce high quality nanocrystals more than 20 years ago. However, template-mediated assembly of colloidal nanocrystals is still at an elementary level, not only because of the limited templates suitable for colloidal assemblies, but also because of the poor control over the assembly of nanocrystals within a confined space. Here, we report the design of a new system called “supracrystalline colloidal eggs” formed by controlled assembly of nanocrystals into complex colloidal supracrystals through superlattice-matched epitaxial overgrowth along the existing colloidosomes. Then, with this concept, we extend the supracrystalline growth to lattice-mismatched binary nanocrystal superlattices, in order to reach anisotropic superlattice growths, yielding freestanding binary nanocrystal supracrystals that could not be produced previously.
Address CEA/IRAMIS , CEA Saclay F-91191 Gif-sur-Yvette, France
Corporate Author Thesis
Publisher Place of Publication Editor
Language English Wos 000372477700034 Publication Date 2016-02-24
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 57 Open Access OpenAccess
Notes The research leading to these results has been supported by an Advanced Grant of the European Research Council under Grant 267129. The authors appreciate financial support by the European Union under the Framework 7 program under a contract for an Integrated Infrastructure Initiative (Reference No. 312483 ESTEEM2). The authors thank Dr. P. A. Albouy for the SAXS measurement.; esteem2_ta Approved Most recent IF: 13.858
Call Number c:irua:131923 c:irua:131923 Serial 4018
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Author Mikita, R.; Aharen, T.; Yamamoto, T.; Takeiri, F.; Ya, T.; Yoshimune, W.; Fujita, K.; Yoshida, S.; Tanaka, K.; Batuk, D.; Abakumov, A.M.; Brown, C.M.; Kobayashi, Y.; Kageyama, H.;
Title Topochemical nitridation with anion vacancy -assisted N3-/O2- exchange Type A1 Journal article
Year 2016 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 138 Issue 138 Pages 3211-3217
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract We present how the introduction of anion vacancies in oxyhydrides enables a route to access new oxynitrides, by conducting ammonolysis of perovskite oxyhydride EuTiO3-xHx (x similar to 0.18). At 400 degrees C, similar to our studies on BaTiO3-xHx, hydride lability enables a low temperature direct ammonolysis of EUTi3.82+O-2.82/H-0.18, leading to the N3-/H--exchanged product EuTi4+O2.82No0.12 square 0.06 center dot When the ammonolysis temperature was increased up to 800 degrees C, we observed a further nitridation involving N3-/O2- exchange, yielding a fully oxidized Eu3+Ti4+O2N with the GdFeO3-type distortion (Pnma) as a metastable phase, instead of pyrochlore structure. Interestingly, the same reactions using the oxide EuTiO3 proceeded through a 1:1 exchange of N3- with O-2 only above 600 degrees C and resulted in incomplete nitridation to EuTi02.25N0.75, indicating that anion vacancies created during the initial nitridation process of EuTiO2.82H0.18 play a crucial role in promoting anion (N3-/O2-) exchange at high temperatures. Hence, by using (hydride-induced) anion-deficient precursors, we should be able to expand the accessible anion composition of perovskite oxynitrides.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000371945800055 Publication Date 2016-02-08
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 28 Open Access
Notes Approved Most recent IF: 13.858
Call Number UA @ lucian @ c:irua:133156 Serial 4266
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Author Polavarapu, L.; Zanaga, D.; Altantzis, T.; Rodal-Cedeira, S.; Pastoriza-Santos, I.; Pérez-Juste, J.; Bals, S.; Liz-Marzán, L.M.
Title Galvanic Replacement Coupled to Seeded Growth as a Route for Shape-Controlled Synthesis of Plasmonic Nanorattles Type A1 Journal article
Year 2016 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 138 Issue 138 Pages 11453-11456
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract Shape-controlled synthesis of metal nanoparticles (NPs) requires mechanistic understanding toward the development of modern nanoscience and nanotechnology. We demonstrate here an unconventional shape transformation of Au@Ag core−shell NPs (nanorods and nanocubes) into octahedral nanorattles via roomtemperature galvanic replacement coupled with seeded growth. The corresponding morphological and chemical transformations were investigated in three dimensions, using state-of-the-art X-ray energy-dispersive spectroscopy (XEDS) tomography. The addition of a reducing agent (ascorbic acid) plays a key role in this unconventional mechanistic path, in which galvanic replacement is found to dominate initially when the shell is made of Ag, while seeded growth suppresses transmetalation when a composition of Au:Ag (∼60:40) is reached in the shell, as revealed by quantitative XEDS tomography. This work not only opens new avenues toward the shape control of hollow NPs beyond the morphology of sacrificial templates, but also expands our understanding of chemical transformations in nanoscale galvanic replacement reactions. The XEDS electron tomography study presented here can be generally applied to investigate a wide range of nanoscale morphological and chemical transformations.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000383410700008 Publication Date 2016-09-14
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 75 Open Access OpenAccess
Notes This work has been funded by the European Research Council (ERC Advanced Grant No. 267867- PLASMAQUO, ERC Starting Grant No. 335078-COLOURATOMS) and Spanish MINECO (Grants MAT2013-45168-R and MAT2013-46101-R); ECAS_Sara; (ROMEO:white; preprint:; postprint:restricted 12 months embargo; pdfversion:cannot); Approved Most recent IF: 13.858
Call Number EMAT @ emat @ c:irua:137123 Serial 4329
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Author Sánchez-Iglesias, A.; Winckelmans, N.; Altantzis, T.; Bals, S.; Grzelczak, M.; Liz-Marzán, L.M.
Title High-Yield Seeded Growth of Monodisperse Pentatwinned Gold Nanoparticles through Thermally Induced Seed Twinning Type A1 Journal article
Year 2016 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 139 Issue 139 Pages 107-110
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract We show here that thermal treatment of small seeds results in extensive twinning and a subsequent drastic yield improvement (>85%) in the formation of pentatwinned nanoparticles, with pre-selected morphology (nanorods, bipyramids and decahedra) and aspect ratio. The “quality” of the seeds thus defines the yield of the obtained nanoparticles, which in the case of nanorods avoids the need for additives such as Ag+ ions. This modified seeded growth method also improves reproducibility, as the seeds can be stored for extended periods of time without compromising the quality of the final nanoparticles. Additionally, minor modification of the seeds with Pd allows their localization within the final particles, which opens new avenues toward mechanistic studies. All together, these results represent a paradigm shift in anisotropic gold nanoparticle synthesis.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000392036900025 Publication Date 2016-12-29
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 267 Open Access OpenAccess
Notes Financial support is acknowledged from the European Research Council through ERC Advanced Grant Plasmaquo and the ERC Starting Grant COLOURATOM. T.A. acknowledges financial support from the Research Foundation Flanders (FWO, Belgium) through a postdoctoral grant. (ROMEO:white; preprint:; postprint:restricted 12 months embargo; pdfversion:cannot); ECAS_Sara Approved Most recent IF: 13.858
Call Number EMAT @ emat @ c:irua:139018UA @ admin @ c:irua:139018 Serial 4339
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Author Kuno, Y.; Tassel, C.; Fujita, K.; Batuk, D.; Abakumov, A.M.; Shitara, K.; Kuwabara, A.; Moriwake, H.; Watabe, D.; Ritter, C.; Brown, C.M.; Yamamoto, T.; Takeiri, F.; Abe, R.; Kobayashi, Y.; Tanaka, K.; Kageyama, H.
Title ZnTaO2N: Stabilized High-Temperature LiNbO3-type Structure Type A1 Journal article
Year 2016 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 138 Issue 138 Pages 15950-15955
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract By using a high-pressure reaction, we prepared a new oxynitride ZnTaO2N that crystallizes in a centrosymmetric (R (3) over barc) high-temperature LiNbO3-type structure (HTLN-type). The stabilization of the HTLN-type structure down to low temperatures (at least 20 K) makes it possible to investigate not only the stability of this phase, but also the phase transition to a noncentrosymmetric (R3c) LiNbO3-type structure (LN-type) which is yet to be clarified. Synchrotron and neutron diffraction studies in combination with transmission electron microscopy show that Zn is located at a disordered 12c site instead of 6a, implying an order disorder mechanism of the phase transition. It is found that the dosed d-shell of Zn2+, as well as the high-valent Ta5+ ion, is responsible for the stabilization of the HTLN-type structure, affording a novel quasitriangular ZnO2N coordination. Interestingly, only 3% Zn substitution for MnTaO2N induces a phase transition from LN- to HTLN-type structure, implying the proximity in energy between the two structural types, which is supported by the first-principles calculations.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000389962800032 Publication Date 2016-11-18
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 13 Open Access
Notes Approved Most recent IF: 13.858
Call Number UA @ lucian @ c:irua:140298 Serial 4452
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Author Wee, L.H.; Meledina, M.; Turner, S.; Van Tendeloo, G.; Zhang, K.; Marleny Rodriguez-Albelo, L.; Masala, A.; Bordiga, S.; Jiang, J.; Navarro, J.A.R.; Kirschhock, C.E.A.; Martens, J.A.
Title 1D-2D-3D Transformation Synthesis of Hierarchical Metal-Organic Framework Adsorbent for Multicomponent Alkane Separation Type A1 Journal article
Year 2017 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 139 Issue 139 Pages 819-828
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract A new hierarchical MOF consisting of Cu(II) centers connected by benzene-tricarboxylates (BTC) is prepared by thermoinduced solid transformation of a dense CuBTC precursor phase. The mechanism of the material formation has been thoroughly elucidated and revealed a transformation of a ribbon-like 1D building unit into 2D layers and finally a 3D network. The new phase contains excess copper, charge compensated by systematic hydroxyl groups, which leads to an open microporous framework with tunable permanent mesoporosity. The new phase is particularly attractive for molecular separation. Energy consumption of adsorptive separation processes can be lowered by using adsorbents that discriminate molecules based on adsorption entropy rather than enthalpy differences. In separation of a 11-component mixture of C-1-C-6 alkanes, the hierarchical phase outperforms the structurally related microporous HKUST-1 as well as silicate-based hierarchical materials. Grand canonical Monte Carlo (GCMC) simulation provides microscopic insight into the structural host-guest interaction, confirming low adsorption enthalpies and significant entropic contributions to the molecular separation. The unique three-dimensional hierarchical structure as well as the systematic presence of Cu(II) unsaturated coordination sites cause this exceptional behavior.
Address
Corporate Author Thesis
Publisher Place of Publication Washington, D.C. Editor
Language Wos 000392459300041 Publication Date 2016-12-15
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 33 Open Access Not_Open_Access
Notes ; L.H.W. and S.T. thank Research Foundation Flanders (FWO) for a postdoctoral research fellowship under contract numbers 12M1415N and G004613N, respectively. J.J. is grateful to the National University of Singapore for financial supports (R261-508-001-646/733 and R-279-000-474-112). J.A.R.N. acknowledges generous funding from Spanish Ministry of Economy (CTQ2014-53486-R) and FEDER and Marie Curie IIF-625939 (L.M.R.A) funding from European Union. J.A.M. gratefully acknowledges financial support from Flemish Government (Long-term structural funding Methusalem). Collaboration among universities was supported by the Belgian Government (IAP-PAI network). We thank E. Gobechiya for XRD measurements. We would like to acknowledge Matthias Thommes for the discussion on the interpretation of N<INF>2</INF> physisorption isotherms. ; Approved Most recent IF: 13.858
Call Number UA @ lucian @ c:irua:141513 c:irua:141513 c:irua:141513 c:irua:141513 Serial 4492
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Author Niu, H.; Pitcher, M.J.; Corkett, A.J.; Ling, S.; Mandal, P.; Zanella, M.; Dawson, K.; Stamenov, P.; Batuk, D.; Abakumov, A.M.; Bull, C.L.; Smith, R.I.; Murray, C.A.; Day, S.J.; Slater, B.; Cora, F.; Claridge, J.B.; Rosseinsky, M.J.
Title Room Temperature Magnetically Ordered Polar Corundum GaFeO3 Displaying Magnetoelectric Coupling Type A1 Journal article
Year 2017 Publication Journal of the American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 139 Issue 4 Pages 1520-1531
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The polar corundum structure type offers a route to new room temperature multiferroic materials, as the partial LiNbO3-type cation ordering that breaks inversion symmetry may be combined with long-range magnetic ordering of high spin d(5) cations above room temperature in the AFeO(3) system. We report the synthesis of a polar corundum GaFeO3 by a high-pressure, high-temperature route and demonstrate that its polarity arises from partial LiNbO3 -type cation ordering by complementary use of neutron, X-ray, and electron diffraction methods. In situ neutron diffraction shows that the polar corundum forms directly from AlFeO3-type GaFeO3 under the synthesis conditions. The A(3+)/Fe3+ cations are shown to be more ordered in polar corundum GaFeO3 than in isostructural ScFeO3. This is explained by DFT calculations which indicate that the extent of ordering is dependent on the configurational entropy available to each system at the very different synthesis temperatures required to form their corundum structures. Polar corundum GaFeO3 exhibits weak ferromagnetism at room temperature that arises from its Fe2O3-like magnetic ordering, which persists to a temperature of 408 K. We demonstrate that the polarity and magnetization are coupled in this system with a measured linear magnetoelectric coupling coefficient of 0.057 ps/m. Such coupling is a prerequisite for potential applications of polar corundum materials in multiferroic/magnetoelectric devices.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000393355600034 Publication Date 2016-12-25
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 12 Open Access OpenAccess
Notes This work was funded by the EPSRC under EP/N004884. We thank the STFC for provision of beam time at ISIS and Diamond Light Source. We thank the Materials Chemistry Consortium (EPSRC, EP/L000202) for access to computer time on the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk). A.M.A. is grateful to the Russian Science Foundation (Grant 14-13-00680) for financial support. MJ.R is a Royal Society Research Professor. We wish to thank Dr. Ming Li (University of Nottingham, UK) for helpful discussion and advice. Original data is available at the University of Liverpool's DataCat repository at DOI: 10.17638/datacat.liverpool.ac.uk/235. The supporting crystallographic information file may also be obtained from FIZ Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany (e-mail: crysdata@fiz-karlsruhe.de), on quoting the deposition number CSD-432419. Approved Most recent IF: 13.858
Call Number EMAT @ emat @c:irua:147507 Serial 4777
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Author Imran, M.; Peng, L.; Pianetti, A.; Pinchetti, V.; Ramade, J.; Zito, J.; Di Stasio, F.; Buha, J.; Toso, S.; Song, J.; Infante, I.; Bals, S.; Brovelli, S.; Manna, L.
Title Halide perovskite-lead chalcohalide nanocrystal heterostructures Type A1 Journal article
Year 2021 Publication Journal Of The American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 143 Issue 3 Pages 1435-1446
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract We report the synthesis of colloidal CsPbX3-Pb4S3Br2 (X = Cl, Br, I) nanocrystal heterostructures, providing an example of a sharp and atomically resolved epitaxial interface between a metal halide perovskite and a non-perovskite lattice. The CsPbBr3-Pb4S3Br2 nanocrystals are prepared by a two-step direct synthesis using preformed subnanometer CsPbBr3 clusters. Density functional theory calculations indicate the creation of a quasi-type II alignment at the heterointerface as well as the formation of localized trap states, promoting ultrafast separation of photogenerated excitons and carrier trapping, as confirmed by spectroscopic experiments. Postsynthesis reaction with either Cl- or I- ions delivers the corresponding CsPbCI3-Pb4S3Br2 and CsPbI3-Pb4S3Br2 heterostructures, thus enabling anion exchange only in the perovskite domain. An increased structural rigidity is conferred to the perovskite lattice when it is interfaced with the chalcohalide lattice. This is attested by the improved stability of the metastable gamma phase (or “black” phase) of CsPbI3 in the CsPbI3-Pb4S3Br2 heterostructure.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000614064400024 Publication Date 2021-01-15
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 54 Open Access OpenAccess
Notes This work was performed on the Dutch national e-infrastructure with the support of SURF Cooperative. L.P. and J.S. are thankful for the support by the National Key R&D Program of China (2018YFC0910600) and the National Natural Science Foundation of China (61775145). F.D.S. and S.B. acknowledge support by the European Research Council via the ERC-StG “NANOLED” (851794) and the ERC-Cog “REALNANO” (815128). The authors acknowledge financial support from the European Commission under the Horizon 2020 Programme through Grant Agreement No. 731019 (EUSMI). S.B., A.P., and V.P. gratefully acknowledge the financial support from the Italian Ministry of University and Research (MIUR) through grant “Dipartimenti di Eccellenza2017 Materials For Energy”.; sygma Approved Most recent IF: 13.858
Call Number UA @ admin @ c:irua:176584 Serial 6726
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Author Bhaskar, G.; Gvozdetskyi, V.; Batuk, M.; Wiaderek, K.M.; Sun, Y.; Wang, R.; Zhang, C.; Carnahan, S.L.; Wu, X.; Ribeiro, R.A.; Bud'ko, S.L.; Canfield, P.C.; Huang, W.; Rossini, A.J.; Wang, C.-Z.; Ho, K.-M.; Hadermann, J.; Zaikina, J., V
Title Topochemical deintercalation of Li from layered LiNiB : toward 2D MBene Type A1 Journal article
Year 2021 Publication Journal Of The American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 143 Issue 11 Pages 4213-4223
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The pursuit of two-dimensional (2D) borides, MBenes, has proven to be challenging, not the least because of the lack of a suitable precursor prone to the deintercalation. Here, we studied room-temperature topochemical deintercalation of lithium from the layered polymorphs of the LiNiB compound with a considerable amount of Li stored in between [NiB] layers (33 at. % Li). Deintercalation of Li leads to novel metastable borides (Li similar to 0.5NiB) with unique crystal structures. Partial removal of Li is accomplished by exposing the parent phases to air, water, or dilute HCl under ambient conditions. Scanning transmission electron microscopy and solid-state Li-7 and B-1(1) NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of (Li similar to 0.5NiB) and the mechanism of Li-deintercalation. We have shown that the deintercalation of Li proceeds via a “zip-lock” mechanism, leading to the condensation of single [NiB] layers into double or triple layers bound via covalent bonds, resulting in structural fragments with Li[NiB](2) and Li[NiB](3) compositions. The crystal structure of Li similar to 0.5NiB is best described as an intergrowth of the ordered single [NiB], double [NiB](2), or triple [NiB](3) layers alternating with single Li layers; this explains its structural complexity. The formation of double or triple [NiB] layers induces a change in the magnetic behavior from temperature-independent paramagnets in the parent LiNiB compounds to the spin-glassiness in the deintercalated Li similar to 0.5NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000634761500021 Publication Date 2021-03-15
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited Open Access Not_Open_Access
Notes Approved Most recent IF: 13.858
Call Number UA @ admin @ c:irua:177697 Serial 6790
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Author Feng, X.; Jena, H.S.; Krishnaraj, C.; Arenas-Esteban, D.; Leus, K.; Wang, G.; Sun, J.; Rüscher, M.; Timoshenko, J.; Roldan Cuenya, B.; Bals, S.; Voort, P.V.D.
Title Creation of Exclusive Artificial Cluster Defects by Selective Metal Removal in the (Zn, Zr) Mixed-Metal UiO-66 Type A1 Journal article
Year 2021 Publication Journal Of The American Chemical Society Abbreviated Journal J Am Chem Soc
Volume Issue Pages jacs.1c05357
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract The differentiation between missing linker defects

and missing cluster defects in MOFs is difficult, thereby limiting the

ability to correlate materials properties to a specific type of defects.

Herein, we present a novel and easy synthesis strategy for the

creation of solely “missing cluster defects” by preparing mixed-metal

(Zn, Zr)-UiO-66 followed by a gentle acid wash to remove the Zn

nodes. The resulting material has the reo UiO-66 structure, typical

for well-defined missing cluster defects. The missing clusters are

thoroughly characterized, including low-pressure Ar-sorption, iDPCSTEM

at a low dose (1.5 pA), and XANES/EXAFS analysis. We

show that the missing cluster UiO-66 has a negligible number of missing linkers. We show the performance of the missing cluster

UiO-66 in CO2 sorption and heterogeneous catalysis.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000730569500001 Publication Date 2021-12-07
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited 29 Open Access OpenAccess
Notes Agentschap Innoveren en Ondernemen, HBC.2019.0110 HBC.2021.0254 ; Universiteit Gent; Fonds Wetenschappelijk Onderzoek, 665501 ; Dalian University of Technology; China Scholarship Council, 201507565009 ; National Natural Science Foundation of China, 22101039 ; H2020 European Research Council, 815128 REALNANO ; sygmaSB Approved Most recent IF: 13.858
Call Number EMAT @ emat @c:irua:183951 Serial 6833
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Author Gonzalez-Nelson, A.; Mula, S.; Simenas, M.; Balciunas, S.; Altenhof, A.R.; Vojvodin, C.S.; Canossa, S.; Banys, J.; Schurko, R.W.; Coudert, F.-X.; van der Veen, M.A.
Title Emergence of coupled rotor dynamics in metal-organic frameworks via tuned steric interactions Type A1 Journal article
Year 2021 Publication Journal Of The American Chemical Society Abbreviated Journal J Am Chem Soc
Volume 143 Issue 31 Pages 12053-12062
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The organic components in metal-organic frameworks (MOFs) are unique: they are embedded in a crystalline lattice, yet, as they are separated from each other by tunable free space, a large variety of dynamic behavior can emerge. These rotational dynamics of the organic linkers are especially important due to their influence over properties such as gas adsorption and kinetics of guest release. To fully exploit linker rotation, such as in the form of molecular machines, it is necessary to engineer correlated linker dynamics to achieve their cooperative functional motion. Here, we show that for MIL-53, a topology with closely spaced rotors, the phenylene functionalization allows researchers to tune the rotors' steric environment, shifting linker rotation from completely static to rapid motions at frequencies above 100 MHz. For steric interactions that start to inhibit independent rotor motion, we identify for the first time the emergence of coupled rotation modes in linker dynamics. These findings pave the way for function-specific engineering of gear-like cooperative motion in MOFs.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000684581100022 Publication Date 2021-07-29
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0002-7863 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.858 Times cited Open Access OpenAccess
Notes Approved Most recent IF: 13.858
Call Number UA @ admin @ c:irua:180504 Serial 6867
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Author Lentijo-Mozo, S.; Tan, R.P.; Garcia-Marcelot, C.; Altantzis, T.; Fazzini, P.F.; Hungria, T.; Cormary, B.; Gallagher, J.R.; Miller, J.T.; Martinez, H.; Schrittwieser, S.; Schotter, J.; Respaud, M.; Bals, S.; Van Tendeloo, G.; Gatel, C.; Soulantica, K.
Title Air- and water-resistant noble metal coated ferromagnetic cobalt nanorods Type A1 Journal article
Year 2015 Publication ACS nano Abbreviated Journal Acs Nano
Volume 9 Issue 9 Pages 2792-2804
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract Cobalt nanorods possess ideal magnetic properties for applications requiring magnetically hard nanoparticles. However, their exploitation is undermined by their sensitivity toward oxygen and water, which deteriorates their magnetic properties. The development of a continuous metal shell inert to oxidation could render them stable, opening perspectives not only for already identified applications but also for uses in which contact with air and/or aqueous media is inevitable. However, the direct growth of a conformal noble metal shell on magnetic metals is a challenge. Here, we show that prior treatment of Co nanorods with a tin coordination compound is the crucial step that enables the subsequent growth of a continuous noble metal shell on their surface, rendering them air- and water-resistant, while conserving the monocrystallity, metallicity and the magnetic properties of the Co core. Thus, the as-synthesized coreshell ferromagnetic nanorods combine high magnetization and strong uniaxial magnetic anisotropy, even after exposure to air and water, and hold promise for successful implementation in in vitro biodiagnostics requiring probes of high magnetization and anisotropic shape.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000351791800055 Publication Date 2015-03-03
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 25 Open Access OpenAccess
Notes 312483 Esteem2; 246791 Countatoms; 335078 Colouratom; esteem2ta; ECASSara; (ROMEO:white; preprint:; postprint:restricted 12 months embargo; pdfversion:cannot); Approved Most recent IF: 13.942; 2015 IF: 12.881
Call Number c:irua:125380 c:irua:125380 Serial 87
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Author Javon, E.; Gaceur, M.; Dachraoui, W.; Margeat, O.; Ackermann, J.; Ilenia Saba, M.; Delugas, P.; Mattoni, A.; Bals, S.; Van Tendeloo, G.
Title Competing forces in the self-assembly of coupled ZnO nanopyramids Type A1 Journal article
Year 2015 Publication ACS nano Abbreviated Journal Acs Nano
Volume 9 Issue 9 Pages 3685-3694
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract Self-assembly (SA) of nanostructures has recently gained increasing interest. A clear understanding of the process is not straightforward since SA of nanoparticles is a complex multiscale phenomenon including different driving forces. Here, we study the SA between aluminum doped ZnO nanopyramids into couples by combining inorganic chemistry and advanced electron microscopy techniques with atomistic simulations. Our results show that the SA of the coupled nanopyramids is controlled first by morphology, as coupling only occurs in the case of pyramids with well-developed facets of the basal planes. The combination of electron microscopy and atomistic modeling reveals that the coupling is further driven by strong ligandligand interaction between the bases of the pyramids as dominant force, while screening effects due to Al doping or solvent as well as corecore interaction are only minor contributions. Our combined approach provides a deeper understanding of the complex interplay between the interactions at work in the coupled SA of ZnO nanopyramids.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000353867000030 Publication Date 2015-03-12
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 21 Open Access OpenAccess
Notes Esmi; 335078 Colouratom; ECAS_Sara; (ROMEO:white; preprint:; postprint:restricted 12 months embargo; pdfversion:cannot); Approved Most recent IF: 13.942; 2015 IF: 12.881
Call Number c:irua:125978 Serial 434
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Author Rossell, M.D.; Abakumov, A.M.; Ramasse, Q.M.; Erni, R.
Title Direct evidence of stacking disorder in the mixed ionic-electronic conductor Sr4Fe6O12+\delta Type A1 Journal article
Year 2013 Publication ACS nano Abbreviated Journal Acs Nano
Volume 7 Issue 4 Pages 3078-3085
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract Determining the structure-to-property relationship of materials becomes particularly challenging when the material under investigation is dominated by defects and structural disorder. Knowledge on the exact atomic arrangement at the defective structure is required to understand its influence on the functional properties. However, standard diffraction techniques deliver structural information that is averaged over many unit cells. In particular, information about defects and order-disorder phenomena is contained in the coherent diffuse scattering intensity which often is difficult to uniquely interpret. Thus, the examination of the local disorder in materials requires a direct method to study their structure on the atomic level with chemical sensitivity. Using aberration-corrected scanning transmission electron microscopy in combination with atomic-resolution electron energy-loss spectroscopy, we show that the controversial structural arrangement of the Fe2O2+delta layers in the mixed ionic-electronic conducting Sr4Fe6O12+delta perovskite can be unambiguously resolved. Our results provide direct experimental evidence for the presence of a nanomixture of “ordered” and “disordered” domains in an epitaxial Sr4Fe6O12+delta thin film. The most favorable arrangement is the disordered structure and is interpreted as a randomly occurring but well-defined local shift of the Fe-O chains in the Fe2O2+delta layers. By analyzing the electron energy-loss near-edge structure of the different building blocks in the Sr4Fe6O12+delta unit cell we find that the mobile holes in this mixed ionic-electronic conducting oxide are highly localized in the Fe2O2+delta layers, which are responsible for the oxide-ion conductivity. A possible link between disorder and oxygen-ion transport along the Fe2O2+delta layers is proposed by arguing that the disorder can effectively break the oxygen diffusion pathways.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000318143300021 Publication Date 2013-03-04
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 4 Open Access
Notes Approved Most recent IF: 13.942; 2013 IF: 12.033
Call Number UA @ lucian @ c:irua:108476 Serial 713
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Author Chen, B.; Sahin, H.; Suslu, A.; Ding, L.; Bertoni, M.I.; Peeters, F.M.; Tongay, S.
Title Environmental changes in MoTe2 excitonic dynamics by defects-activated molecular interaction Type A1 Journal article
Year 2015 Publication ACS nano Abbreviated Journal Acs Nano
Volume 9 Issue 9 Pages 5326-5332
Keywords A1 Journal article; Engineering sciences. Technology; Condensed Matter Theory (CMT)
Abstract Monolayers of group VI transition metal dichalcogenides possess direct gaps in the visible spectrum with the exception of MoTe2, where its gap is suitably located in the infrared region but its stability is of particular interest, as tellurium compounds are acutely sensitive to oxygen exposure. Here, our environmental (time-dependent) measurements reveal two distinct effects on MoTe2 monolayers: For weakly luminescent monolayers, photoluminescence signal and optical contrast disappear, as if they are decomposed, but yet remain intact as evidenced by AFM and Raman measurements. In contrast, strongly luminescent monolayers retain their optical contrast for a prolonged amount of time, while their PL peak blue-shifts and PL intensity saturates to slightly lower values. Our X-ray photoelectron spectroscopy measurements and DFT calculations suggest that the presence of defects and functionalization of these defect sites with O-2 molecules strongly dictate their material properties and aging response by changing the excitonic dynamics due to deep or shallow states that are created within the optical band gap. Presented results not only shed light on environmental effects on fundamental material properties and excitonic dynamics of MoTe2 monolayers but also highlight striking material transformation for metastable 20 systems such as WTe2, silicone, and phosphorene.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000355383000068 Publication Date 2015-04-14
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 150 Open Access
Notes ; This work was supported by the Arizona State University seeding program. The authors thank Hui Cai and Kedi Wu for useful discussions. We gratefully acknowledge the use of facilities at the LeRoy Eyring Center for Solid State Science at Arizona State University. This work was supported by the Flemish Science Foundation (FWO-VI) and the Methusalem Foundation of the Flemish government. H.S. is supported by a FWO Pegasus Long Marie Curie Fellowship. ; Approved Most recent IF: 13.942; 2015 IF: 12.881
Call Number c:irua:126441 Serial 1068
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Author Sanz-Ortiz, M.N.; Sentosun, K.; Bals, S.; Liz-Marzan, L.M.
Title Templated Growth of Surface Enhanced Raman Scattering -Active Branched Au Nanoparticles within Radial Mesoporous Silica Shells Type A1 Journal article
Year 2015 Publication ACS nano Abbreviated Journal Acs Nano
Volume 9 Issue 9 Pages 10489-10497
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract Noble metal nanoparticles are widely used as probes or substrates for surface-enhanced Raman scattering (SERS), due to their characteristic plasmon resonances in the visible and NIR spectral ranges. Aiming at obtaining a versatile system with high SERS performance we developed the synthesis of quasi-monodisperse, non-aggregated gold nanoparticles protected by radial mesoporous silica shells. The radial channels of such shells were used as templates for the growth of gold tips branching from the cores, thereby improving the plasmonic performance of the particles while favoring the localization of analyte molecules at high electric field regions: close to the tips, inside the pores. The method, which allows control over tip length, was successfully applied to various gold nanoparticle shapes, leading to materials with highly efficient SERS performance. The obtained nanoparticles are stable in ethanol and water upon thermal consolidation and can be safely stored as a powder.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language English Wos 000363915300105 Publication Date 2015-09-15
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 110 Open Access OpenAccess
Notes This work has been funded by the European Research Council (ERC Advanced Grant 267867 Plasmaquo and Starting Grant Colouratom). The research leading to these results has received funding from the European Union's Seventh Framework Programme (FP7/2007-2013 under grant agreement no. 312184, SACS). Help from Mert Kurttepeli is acknowledged. Pentatwinned nanorods and nanotriangles were synthesized by L. Scarabelli.; ECAS_Sara; (ROMEO:white; preprint:; postprint:restricted 12 months embargo; pdfversion:cannot); Approved Most recent IF: 13.942; 2015 IF: 12.881
Call Number c:irua:129194 Serial 3947
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Author Tognalii, N.G.; Cortés, E.; Hernández-Nieves, A.D.; Carro, P.; Usaj, G.; Balseiro, C.A.; Vela, M.E.; Salvarezza, R.C.; Fainstein, A.
Title From single to multiple Ag-layer modification of Au nanocavity substrates : a tunable probe of the chemical surface-enhanced Raman scattering mechanism Type A1 Journal article
Year 2011 Publication ACS nano Abbreviated Journal Acs Nano
Volume 5 Issue 7 Pages 5433-5443
Keywords A1 Journal article; Condensed Matter Theory (CMT)
Abstract We present experimental and computational results that enlighten the mechanisms underlying the chemical contribution to surface-enhanced Raman scattering (SERS). Gold void metallic arrays electrochemically covered either by a Ag monolayer or 10100 Ag layers were modified with a self-assembled monolayer of 4-mercaptopyridine as a molecular Raman probe displaying a rich and unexpected Raman response. A resonant increase of the Raman intensity in the red part of the spectrum is observed that cannot be related to plasmon excitations of the cavity-array. Notably, we find an additional 1020 time increase of the SERS amplification upon deposition of a single Ag layer on the Au substrate, which is, however, almost quenched upon deposition of 10 atomic layers. Further deposition of 100 atomic Ag layers results in a new increase of the SERS signal, consistent with the improved plasmonic efficiency of Ag bulk-like structures. The SERS response as a function of the Ag layer thickness is analyzed in terms of ab initio calculations and a microscopic model for the SERS chemical mechanism based on a resonant charge transfer process between the molecular HOMO state and the Fermi level in the metal surface. We find that a rearrangement of the electronic charge density related to the presence of the Ag monolayer in the Au/Ag/molecule complex causes an increase in the distance between the HOMO center of charge and the metallic image plane that is responsible for the variation of Raman enhancement between the studied substrates. Our results provide a general platform for studying the chemical contribution to SERS, and for enhancing the Raman efficiency of tailored Au-SERS templates through electrochemical modification with Ag films.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000293035200019 Publication Date 2011-06-15
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 26 Open Access
Notes ; We acknowledge financial support from ANPCyT (Argentina, PICT08-1617, PICT08-2236, PICT06-621, PICT-CNPQ-08-0019, PAE 22711, PICT06-01061, PICT06-483) and Project CTQ2008-06017/BQU, Spain. N.G.T, E.C., A.D.H.N., R.C.S, G.U., C.A.B., and A.F. are also at CONICET. M.E.V. is a member of the research career of CIC BsAs. R.C.S., C.A.B., and A.F. are Guggenheim Foundation Fellows. We would like to thank Dr. M. H. Fonticelli for fruitful discussions on the electrochemical measurements and Dr. H. Pastoriza for the help with the SEM measurements. ; Approved Most recent IF: 13.942; 2011 IF: 11.421
Call Number UA @ lucian @ c:irua:91775 Serial 1285
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Author Sánchez-Iglesias, A.; Grzelczak, M.; Altantzis, T.; Goris, B.; Pérez-Juste, J.; Bals, S.; Van Tendeloo, G.; Donaldson, S.H.; Chmelka, B.F.; Israelachvili, J.N.; Liz-Marzán, L.M.;
Title Hydrophobic interactions modulate self-assembly of nanoparticles Type A1 Journal article
Year 2012 Publication ACS nano Abbreviated Journal Acs Nano
Volume 6 Issue 12 Pages 11059-11065
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract Hydrophobic interactions constitute one of the most important types of nonspecific interactions in biological systems, which emerge when water molecules rearrange as two hydrophobic species come close to each other. The prediction of hydrophobic interactions at the level of nanoparticles (Brownian objects) remains challenging because of uncontrolled diffusive motion of the particles. We describe here a general methodology for solvent-induced, reversible self-assembly of gold nanoparticles into 3D clusters with well-controlled sizes. A theoretical description of the process confirmed that hydrophobic interactions are the main driving force behind nanoparticle aggregation.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000312563600070 Publication Date 2012-11-28
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 311 Open Access
Notes 267867 Plasma Quo; 246791 Countatoms; 262348 Esmi Approved Most recent IF: 13.942; 2012 IF: 12.062
Call Number UA @ lucian @ c:irua:105292 Serial 1538
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Author Quintana, M.; López, A.M.; Rapino, S.; Toma, F.M.; Iurlo, M.; Carraro, M.; Sartorel, A.; Maccato, C.; Ke, X.; Bittencourt, C.; Da Ros, T.; Van Tendeloo, G.; Marcaccio, M.; Paolucci, F.; Prato, M.; Bonchio, M.;
Title Knitting the catalytic pattern of artificial photosynthesis to a hybrid graphene nanotexture Type A1 Journal article
Year 2013 Publication ACS nano Abbreviated Journal Acs Nano
Volume 7 Issue 1 Pages 811-817
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract The artificial leaf project calls for new materials enabling multielectron catalysis with minimal overpotential, high turnover frequency, and long-term stability. Is graphene a better material than carbon nanotubes to enhance water oxidation catalysis for energy applications? Here we show that functionalized graphene with a tailored distribution of polycationic, quaternized, ammonium pendants provides an sp(2) carbon nanoplatform to anchor a totally inorganic tetraruthenate catalyst, mimicking the oxygen evolving center of natural PSII. The resulting hybrid material displays oxygen evolution at overpotential as low as 300 mV at neutral pH with negligible loss of performance after 4 h testing. This multilayer electroactive asset enhances the turnover frequency by 1 order of magnitude with respect to the isolated catalyst, and provides a definite up-grade of the carbon nanotube material, with a similar surface functionalization. Our innovation is based on a noninvasive, synthetic protocol for graphene functionalization that goes beyond the ill-defined oxidation-reduction methods, allowing a definite control of the surface properties.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000314082800088 Publication Date 2012-12-17
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 69 Open Access
Notes 246791 COUNTATOMS; 262348 ESMI; ESF Cost Action NanoTP MP0901 Approved Most recent IF: 13.942; 2013 IF: 12.033
Call Number UA @ lucian @ c:irua:107707 Serial 1766
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Author Quintana, M.; Ke, X.; Van Tendeloo, G.; Meneghetti, M.; Bittencourt, C.; Prato, M.
Title Light-induced selective deposition of Au nanoparticles on single-wall carbon nanotubes Type A1 Journal article
Year 2010 Publication ACS nano Abbreviated Journal Acs Nano
Volume 4 Issue 10 Pages 6105-6113
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract Novel applications of single-walled carbon nanotubes (SWNT) rely on the development of new strategies to make them easier to handle without affecting their structural properties. In this work, we have selectively deposited Au nanoparticles (Au NP) on SWNT assisted by UV light irradiation. XPS analysis and UV-vis spectroscopy indicate that the deposition occurs at the defects generated after oxidation of the SWNT. By addition of n-dodecylthiol, the separation of oxidized tubes with Au NP (Au-ox-SWNT) from tubes devoid of Au NP (bare tubes, b-SWNT) was achieved. Raman and UV-vis-NIR spectra indicate that UV irradiation induces a faster nucleation of Au NP on metallic SWNT. This new technique can be useful for the preparation of nanohybrid composites with enhanced properties, as increased thermal stability, and to obtain purified SWNT.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000283453700081 Publication Date 2010-09-24
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 26 Open Access
Notes Approved Most recent IF: 13.942; 2010 IF: 9.865
Call Number UA @ lucian @ c:irua:99202 Serial 1819
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Author Walter, A.L.; Sahin, H.; Jeon, K.J.; Bostwick, A.; Horzum, S.; Koch, R.; Speck, F.; Ostler, M.; Nagel, P.; Merz, M.; Schupler, S.; Moreschini, L.; Chang, Y.J.; Seyller, T.; Peeters, F.M.; Horn, K.; Rotenberg, E.;
Title Luminescence, patterned metallic regions, and photon-mediated electronic changes in single-sided fluorinated graphene sheets Type A1 Journal article
Year 2014 Publication ACS nano Abbreviated Journal Acs Nano
Volume 8 Issue 8 Pages 7801-7808
Keywords A1 Journal article; Engineering sciences. Technology; Condensed Matter Theory (CMT)
Abstract Single-sided fluorination has been predicted to open an electronic band gap in graphene and to exhibit unique electronic and magnetic properties; however, this has not been substantiated by experimental reports. Our comprehensive experimental and theoretical study of this material on a SiC(0001) substrate shows that single-sided fluorographene exhibits two phases, a stable one with a band gap of similar to 6 eV and a metastable one, induced by UV irradiation, with a band gap of similar to 2.5 eV. The metastable structure, which reverts to the stable “ground-state” phase upon annealing under emission of blue light, in our view is induced by defect states, based on the observation of a nondispersive electronic state at the top of the valence band, not unlike that found in organic molecular layers. Our structural data show that the stable C2F ground state has a “boat” structure, in agreement with our X-ray magnetic circular dichroism data, which show the absence of an ordered magnetic phase. A high flux of UV or X-ray photons removes the fluorine atoms, demonstrating the possibility of lithographically patterning conducting regions into an otherwise semiconducting 2D material.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000340992300025 Publication Date 2014-08-09
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 23 Open Access
Notes Approved Most recent IF: 13.942; 2014 IF: 12.881
Call Number UA @ lucian @ c:irua:119263 Serial 1857
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Author Felten, A.; Gillon, X.; Gulas, M.; Pireaux, J.-J.; Ke, X.; Van Tendeloo, G.; Bittencourt, C.; Najafi, E.; Hitchcock, A.P.
Title Measuring point defect density in individual carbon nanotubes using polarization-dependent X-ray microscopy Type A1 Journal article
Year 2010 Publication ACS nano Abbreviated Journal Acs Nano
Volume 4 Issue 8 Pages 4431-4436
Keywords A1 Journal article; Electron microscopy for materials research (EMAT)
Abstract The presence of defects in carbon nanotubes strongly modifies their electrical, mechanical, and chemical properties. It was long thought undesirable, but recent experiments have shown that introduction of structural defects using ion or electron irradiation can lead to novel nanodevices. We demonstrate a method for detecting and quantifying point defect density in individual carbon nanotubes (CNTs) based on measuring the polarization dependence (linear dichroism) of the C 1s → π* transition at specific locations along individual CNTs with a scanning transmission X-ray microscope (STXM). We show that STXM can be used to probe defect density in individual CNTs with high spatial resolution. The quantitative relationship between ion dose, nanotube diameter, and defect density was explored by purposely irradiating selected sections of nanotubes with kiloelectronvolt (keV) Ga+ ions. Our results establish polarization-dependent X-ray microscopy as a new and very powerful characterization technique for carbon nanotubes and other anisotropic nanostructures.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language Wos 000281052700014 Publication Date 2010-07-07
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 26 Open Access
Notes Approved Most recent IF: 13.942; 2010 IF: 9.865
Call Number UA @ lucian @ c:irua:84734 Serial 1966
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Author Yan, Y.; Zhou, X.; Jin, H.; Li, C.-Z.; Ke, X.; Van Tendeloo, G.; Liu, K.; Yu, D.; Dressel, M.; Liao, Z.-M.
Title Surface-Facet-Dependent Phonon Deformation Potential in Individual Strained Topological Insulator Bi2Se3 Nanoribbons Type A1 Journal article
Year 2015 Publication ACS nano Abbreviated Journal Acs Nano
Volume 9 Issue 9 Pages 10244-10251
Keywords A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Abstract Strain is an important method to tune the properties of topological insulators. For example, compressive strain can induce superconductivity in Bi2Se3 bulk material. Topological insulator nanostructures are the superior candidates to utilize the unique surface states due to the large surface to volume ratio. Therefore, it is highly desirable to monitor the local strain effects in individual topological insulator nanostructures. Here, we report the systematical micro-Raman spectra of single strained Bi2Se3 nanoribbons with different thicknesses and different surface facets, where four optical modes are resolved in both Stokes and anti-Stokes Raman spectral lines. A striking anisotropy of the strain dependence is observed in the phonon frequency of strained Bi2Se3 nanoribbons grown along the ⟨112̅0⟩ direction. The frequencies of the in-plane Eg2 and out-of-plane A1g1 modes exhibit a nearly linear blue-shift against bending strain when the nanoribbon is bent along the ⟨112̅0⟩ direction with the curved {0001} surface. In this case, the phonon deformation potential of the Eg2 phonon for 100 nm-thick Bi2Se3 nanoribbon is up to 0.94 cm–1/%, which is twice of that in Bi2Se3 bulk material (0.52 cm–1/%). Our results may be valuable for the strain modulation of individual topological insulator nanostructures.
Address
Corporate Author Thesis
Publisher Place of Publication Editor
Language English Wos 000363915300079 Publication Date 2015-09-12
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 1936-0851;1936-086X; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor (up) 13.942 Times cited 14 Open Access
Notes Y.Y. would like to thank Xuewen Fu for helpful discussions. This work was supported by MOST (Nos. 2013CB934600, 2013CB932602) and NSFC (Nos. 11274014, 11234001). Approved Most recent IF: 13.942; 2015 IF: 12.881
Call Number c:irua:129216 Serial 3963
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