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  • 1.
    Aleksis, Rihards
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Carvalho, José P.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Artefact-free broadband 2D NMR for separation of quadrupolar and paramagnetic shift interactions2019In: Solid State Nuclear Magnetic Resonance, ISSN 0926-2040, E-ISSN 1527-3326, Vol. 101, p. 51-62Article in journal (Refereed)
    Abstract [en]

    Two new two-dimensional, broadband, solid-state NMR experiments for separating and correlating the quadrupolar and shift interactions of spin I = 1 nuclei in paramagnetic systems are proposed. The new pulse sequences incorporate the short, high-power adiabatic pulses (SHAPs) into the shifting d-echo experiment of Walder et al. [J. Chem. Phys., 142, 014201 (2015)], in two different ways, giving double and quadruple adiabatic shifting d-echo sequences. These new experiments have the advantage over previous methods of both suppressing spectral artefacts due to pulse imperfections, and exhibiting a broader excitation bandwidth. Both experiments are analysed with theoretical calculations and simulations, and are applied experimentally to the H-2 NMR of deuterated CuCl2 center dot 2H(2)O, and two deuterated samples of the ion conductor oxyhydride BaTiO3-xHy prepared using two different methods. For the CuCl2 center dot 2H(2)O sample, both new methods obtain very high-quality spectra from which the parameters describing the shift and quadrupolar interaction tensors, and their relative orientation, were extracted. The two BaTiO3-xHy samples exhibited different local hydride environments with different tensor parameters. The H-2 spectra of these oxyhydrides exhibit inhomogeneous broadening of the H-2 shifts, and so whilst the quadrupolar interaction parameters were easily extracted, the measurement of the shift parameters was more complex. However, effective shift parameters were extracted, which combine the effects of both the paramagnetic shift tensor and the inhomogeneous broadening.

  • 2. Brant, William R.
    et al.
    Mogensen, Ronnie
    Colbin, Simon
    Ojwang, Dickson O.
    Schmid, Siegbert
    Häggström, Lennart
    Ericsson, Tore
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Younesi, Reza
    Selective Control of Composition in Prussian White for Enhanced Material Properties2019In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 31, no 18, p. 7203-7211Article in journal (Refereed)
    Abstract [en]

    Sodium-ion batteries based on Prussian blue analogues (PBAs) are ideal for large-scale energy storage applications due to the ability to meet the huge volumes and low costs required. For Na2-xFe[Fe(CN)(6)](1-y)center dot zH(2)O, realizing its commercial potential means fine control of the concentration of sodium, Fe(CN)(6) vacancies, and water content. To date, there is a huge variation in the literature of composition leading to variable electrochemical performance. In this work, we break down the synthesis of PBAs into three steps for controlling the sodium, vacancy, and water content via an inexpensive, scalable synthesis method. We produce rhombohedral Prussian white Na1.88(5)Fe[Fe-(CN)(6)]center dot 0.18(9)H2O with an initial capacity of 158 mAh/g retaining 90% capacity after 50 cycles. Subsequent characterization revealed that the increased polarization on the 3 V plateau is coincident with a phase transition and reduced utilization of the high-spin Fe(III)/Fe(II) redox couple. This reveals a clear target for subsequent improvements of the material to boost long-term cycling stability. These results will be of great interest for the myriad of applications of PBAs, such as catalysis, magnetism, electrochromics, and gas sorption.

  • 3. D'Anna, V.
    et al.
    Norsic, S.
    Gajan, D.
    Sanders, K.
    Pell, Andrew J.
    Université de Lyon, France.
    Lesage, A.
    Monteil, V.
    Copéret, C.
    Pintacuda, G.
    Sautet, P.
    Structural Characterization of the EtOH–TiCl4–MgCl2 Ziegler–Natta Precatalyst2016In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 120, no 32, p. 18075-18087Article in journal (Refereed)
  • 4.
    Eklöf, Daniel
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Fischer, Andreas
    Ektarawong, Annop
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Grins, Jekabs
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Simak, Sergei
    Alling, Björn
    Wu, Yang
    Widom, Michael
    Scherer, Wolfgang
    Häussermann, Ulrich
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Mysterious SiB3: Identifying the Relation between α- and β-SiB32019In: ACS omega, ISSN 2470-1343, Vol. 4, no 20, p. 18741-18759Article in journal (Refereed)
    Abstract [en]

    Binary silicon boride SiB3 has been reported to occur in two forms, as disordered and nonstoichiometric alpha-SiB3-x, which relates to the alpha-rhombohedral phase of boron, and as strictly ordered and stoichiometric beta-SiB3. Similar to other boron-rich icosahedral solids, these SiB3 phases represent potentially interesting refractory materials. However, their thermal stability, formation conditions, and thermodynamic relation are poorly understood. Here, we map the formation conditions of alpha-SiB3-x and beta-SiB3 and analyze their relative thermodynamic stabilities. alpha-SiB3-x is metastable (with respect to beta-SiB3 and Si), and its formation is kinetically driven. Pure polycrystalline bulk samples may be obtained within hours when heating stoichiometric mixtures of elemental silicon and boron at temperatures 1200-1300 degrees C. At the same time, alpha-SiB3-x decomposes into SiB6 and Si, and optimum time-temperature synthesis conditions represent a trade-off between rates of formation and decomposition. The formation of stable beta-SiB3 was observed after prolonged treatment (days to weeks) of elemental mixtures with ratios Si/B = 1:11:4 at temperatures 1175-1200 degrees C. The application of high pressures greatly improves the kinetics of SiB3 formation and allows decoupling of SiB3 formation from decomposition. Quantitative formation of beta-SiB3 was seen at 1100 degrees C for samples pressurized to 5.5-8 GPa. beta-SiB3 decomposes peritectoidally at temperatures between 1250 and 1300 degrees C. The highly ordered nature of beta-SiB3 is reflected in its Raman spectrum, which features narrow and distinct lines. In contrast, the Raman spectrum of alpha-SiB3-x is characterized by broad bands, which show a clear relation to the vibrational modes of isostructural, ordered B6P. The detailed composition and structural properties of disordered alpha-SiB3-x were ascertained by a combination of single-crystal X-ray diffraction and Si-29 magic angle spinning NMR experiments. Notably, the compositions of polycrystalline bulk samples (obtained at T <= 1200 degrees C) and single crystal samples (obtained from Si-rich molten Si-B mixtures at T > 1400 degrees C) are different, SiB2.93(7) and SiB2.64(2), respectively. The incorporation of Si in the polar position of B-12 icosahedra results in highly strained cluster units. This disorder feature was accounted for in the refined crystal structure model by splitting the polar position into three sites. The electron-precise composition of alpha-SiB3-x is SiB2.5 and corresponds to the incorporation of, on average, two Si atoms in each B-12 icosahedron. Accordingly, alpha-SiB3-x constitutes a mixture of B10Si2 and B11Si clusters. The structural and phase stability of alpha-SiB3-x were explored using a first-principles cluster expansion. The most stable composition at 0 K is SiB2.5, which however is unstable with respect to the decomposition beta-SiB3 + Si. Modeling of the configurational and vibrational entropies suggests that alpha-SiB3-x only becomes more stable than beta-SiB3 at temperatures above its decomposition into SiB6 and Si. Hence, we conclude that alpha-SiB3-x is metastable at all temperatures. Density functional theory electronic structure calculations yield band gaps of similar size for electron-precise alpha-SiB2.5 and beta-SiB3, whereas alpha-SiB3 represents a p-type conductor.

  • 5. Eklöf-Österberg, Carin
    et al.
    Nedumkandathil, Reji
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Häussermann, Ulrich
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Tyagi, Madhusudan
    Jalarvo, Niina H.
    Frick, Bernhard
    Faraone, Antonio
    Karlsson, Maths
    Dynamics of Hydride Ions in Metal Hydride-Reduced BaTiO3 Samples Investigated with Quasielastic Neutron Scattering2019In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 123, no 4, p. 2019-2030Article in journal (Refereed)
    Abstract [en]

    Perovskite-type oxyhydrides, BaTiO3-xHx, have been recently shown to exhibit hydride-ion (H-) conductivity at elevated temperatures, but the underlying mechanism of hydride-ion conduction and how it depends on temperature and oxygen vacancy concentration remains unclear. Here, we investigate, through the use of quasielastic neutron scattering techniques, the nature of the hydride-ion dynamics in three metal hydride-reduced BaTiO3 samples that are characterized by the simultaneous presence of hydride ions and oxygen vacancies. Measurements of elastic fixed window scans upon heating reveal the presence of quasielastic scattering due to hydride-ion dynamics for temperatures above ca. 200 K. Analyses of quasielastic spectra measured at low (225 and 250 K) and high (400-700 K) temperature show that the dynamics can be adequately described by established models of jump diffusion. At low temperature, <= 250 K, all of the models feature a characteristic jump distance of about 2.8 angstrom, thus of the order of the distance between neighboring oxygen atoms or oxygen vacancies of the perovskite lattice and a mean residence time between successive jumps of the order of 0.1 ns. At higher temperatures, >400 K, the jump distance increases to about 4 angstrom, thus of the order of the distance between next-nearest neighboring oxygen atoms or oxygen vacancies, with a mean residence time of the order of picoseconds. A diffusion constant D was computed from the data measured at low and high temperatures, respectively, and takes on values of about 0.4 X 10(-6) cm(-2) s(-1) at the lowest applied temperature of 225 K and between ca. 20 X 10(-6) and 100 X 10(-6) cm(-2) s(-1) at temperatures between 400 and 700 K. Activation energies E-a were derived from the measurements at high temperatures and take on values of about 0.1 eV and show a slight increase with increasing oxygen vacancy concentration.

  • 6.
    Etman, Ahmed S.
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Alexandria University, Egypt.
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Svedlindh, Peter
    Hedin, Niklas
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Zou, Xiaodong
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Sun, Junliang
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Peking University, China.
    Bernin, Diana
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Chalmers University of Technology, Sweden.
    Insights into the Exfoliation Process of V2O5 center dot nH(2)O Nanosheet Formation Using Real-Time V-51 NMR2019In: Acs Omega, ISSN 2470-1343, Vol. 4, no 6, p. 10899-10905Article in journal (Refereed)
    Abstract [en]

    Nanostructured hydrated vanadium oxides (V2O5 center dot nH(2)O) are actively being researched for applications in energy storage, catalysis, and gas sensors. Recently, a one-step exfoliation technique for fabricating V2O5 center dot nH(2)O nano-sheets in aqueous media was reported; however, the underlying mechanism of exfoliation has been challenging to study. Herein, we followed the synthesis of V2O5 center dot nH(2)O nanosheets from the V2O5 and VO2 precursors in real using solution- and solid-state V-51 NMR. Solution-state V-51 NMR showed that the aqueous solution contained mostly the decavanadate anion [H2V10O28](4-) and the hydrated dioxova-nadate cation [VO2 center dot 4H(2)O](+), and during the exfoliation process, decavanadate was formed, while the amount of [VO2 center dot 4H(2)O](+) remained constant. The conversion of the solid precursor V2O5, which was monitored with solid-state V-51 NMR, was initiated when VO2 was in its monoclinic forms. The dried V2O5 center dot nH(2)O nanosheets were weakly paramagnetic because of a minor content of isolated V4+. Its solid-state V-51 signal was less than 20% of V2O5 and arose from diamagnetic V4+ or V5+.This study demonstrates the use of real-time NMR techniques as a powerful analysis tool for the exfoliation of bulk materials into nanosheets. A deeper understanding of this process will pave the way to tailor these important materials.

  • 7. George, Nathan C.
    et al.
    Brgoch, Jakoah
    Pell, Andrew J.
    Université de Lyon, France.
    Cozzan, Clayton
    Jaffe, Adam
    Dantelle, Géraldine
    Llobet, Anna
    Pintacuda, Guido
    Seshadri, Ram
    Chmelka, Bradley F.
    Correlating Local Compositions and Structures with the Macroscopic Optical Properties of Ce3+-Doped CaSc2O4, an Efficient Green-Emitting Phosphor2017In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 29, no 8, p. 3538-3546Article in journal (Refereed)
  • 8. Jaudzems, Kristaps
    et al.
    Bertarello, Andrea
    Chaudhari, Sachin R.
    Pica, Andrea
    Cala-De Paepe, Diane
    Barbet-Massin, Emeline
    Pell, Andrew J.
    Université de Lyon, France.
    Akopjana, Inara
    Kotelovica, Svetlana
    Gajan, David
    Ouari, Olivier
    Tars, Kaspars
    Pintacuda, Guido
    Lesage, Anne
    Dynamic Nuclear Polarization‐Enhanced Biomolecular NMR Spectroscopy at High Magnetic Field with Fast Magic‐Angle Spinning2018In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 57, no 25, p. 7458-7462Article in journal (Refereed)
  • 9. Lee, Jeongjae
    et al.
    Seymour, Ieuan D.
    Pell, Andrew J.
    University of Cambridge, United Kingdom.
    Dutton, Sian E.
    Grey, Clare P.
    A systematic study of 25Mg NMR in paramagnetic transition metal oxides: applications to Mg-ion battery materials2017In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 19, no 1, p. 613-625Article in journal (Refereed)
  • 10. Ma, Zili
    et al.
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    George, Janine
    Rokicinska, Anna
    Thersleff, Thomas
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Budnyak, Tetyana M.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Hautier, Geoffroy
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Dronskowski, Richard
    Kustrowski, Piotr
    Slabon, Adam
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Exploring the Origins of Improved Photocurrent by Acidic Treatment for Quaternary Tantalum-Based Oxynitride Photoanodes on the Example of CaTaO2N2020In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 124, no 1, p. 152-160Article in journal (Refereed)
    Abstract [en]

    Quaternary tantalum-based oxynitrides ATa(O,N)3, with electronic band gaps between 1.8 and 2.4 eV, are promising materials for photochemical water-splitting. The tailoring of their surface properties is a critical aspect to obtain efficient hole extraction. We report on the origin of improved photoelectrochemical (PEC) water oxidation by means of acidic treatment for this class of compounds on the example of cubic CaTaO2N particles. We address the effect of acidic treatment by using complementary physical characterization techniques, such as X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, 1H and 14N solid-state nuclear magnetic resonance (NMR) spectroscopy, electron microscopy, and electronic band structure calculations at the density functional theory level. In combination with PEC measurements, solid-state NMR indicates that the restructured surface displays a meaningfully higher concentration of terminating OH groups. Subsequent deposition of a nickel borate (NiBi) catalyst on the acid-treated surface yields a higher percentual upsurge of photocurrent in comparison to pristine CaTaO2N. Our results highlight the application of solid-state NMR spectroscopy for understanding the semiconductor–catalyst interface in photochemical devices.

  • 11. Michan, Alison L.
    et al.
    Divitini, Georgio
    Pell, Andrew J.
    University of Cambridge, United Kingdom.
    Leskes, Michal
    Ducati, Caterina
    Grey, Clare P.
    Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes2016In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 138, no 25, p. 7918-7931Article in journal (Refereed)
  • 12.
    Mitoudi-Vagourdi, Eleni
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Papawassiliou, Wassilios
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Müllner, Silvia
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Lemmens, Peter
    Kremer, Reinhard K.
    Johnsson, Mats
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Synthesis and Physical Properties of the Oxofluoride Cu-2(SeO3)F-22018In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 57, no 8, p. 4640-4648Article in journal (Refereed)
    Abstract [en]

    Single crystals of the new compound Cu-2(SeO3)F-2 were successfully synthesized via a hydrothermal method, and the crystal structure was determined from single-crystal X-ray diffraction data. The compound crystallizes in the orthorhombic space group Pnma with the unit cell parameters a = 7.066(4) (A) over circle, b = 9.590(4) (A) over circle, and c = 5.563(3) (A) over circle. Cu-2(SeO3)F-2 is isostructural with the previously described compounds Co2TeO3F2 and CoSeO3F2. The crystal structure comprises a framework of corner- and edge-sharing distorted [CuO3F3] octahedra, within which [SeO3] trigonal pyramids are present in voids and are connected to [CuO3F3] octahedra by corner sharing. The presence of a single local environment in both the F-19 and Se-77 solid-state MAS NMR spectra supports the hypothesis that O and F do not mix at the same crystallographic positions. Also the specific phonon modes observed with Raman scattering support the coordination around the cations. At high temperatures the magnetic susceptibility follows the Curie-Weiss law with Curie temperature of Theta = -173(2) K and an effective magnetic moment of mu(eff) similar to 2.2 mu(B). Antiferromagnetic ordering below similar to 44 K is indicated by a peak in the magnetic susceptibility. A second though smaller peak at similar to 16 K is tentatively ascribed to a magnetic reorientation transition. Both transitions are also confirmed by heat capacity measurements. Raman scattering experiments propose a structural phase instability in the temperature range 6-50 K based on phonon anomalies. Further changes in the Raman shift of modes at similar to 46 K and similar to 16 K arise from transitions of the magnetic lattice in accordance with the susceptibility and heat capacity measurements.

  • 13. Mondal, Arobendo
    et al.
    Gaultois, Michael W.
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Iannuzzi, Marcella
    Grey, Clare P.
    Hutter, Jürg
    Kaupp, Martin
    Large-Scale Computation of Nuclear Magnetic Resonance Shifts for Paramagnetic Solids Using CP2K2018In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 14, no 1, p. 377-394Article in journal (Refereed)
    Abstract [en]

    Large-scale computations of nuclear magnetic resonance (NMR) shifts for extended paramagnetic solids (pNMR) are reported using the highly efficient Gaussian-augmented plane-wave implementation of the CP2K code. Combining hyperfine couplings obtained with hybrid functionals with g-tensors and orbital shieldings computed using gradient-corrected functionals, contact, pseudocontact, and orbital-shift contributions to pNMR shifts are accessible. Due to the efficient and highly parallel performance of CP2K, a wide variety of materials with large unit cells can be studied with extended Gaussian basis sets. Validation of various approaches for the different contributions to pNMR shifts is done first for molecules in a large supercell in comparison with typical quantum-chemical codes. This is then extended to a detailed study of g-tensors for extended solid transition-metal fluorides and for a series of complex lithium vanadium phosphates. Finally, lithium pNMR shifts are computed for Li3V2(PO4)(3), for which detailed experimental data are available. This has allowed an in-depth study of different approaches (e.g., full periodic versus incremental cluster computations of g-tensors and different functionals and basis sets for hyperfine computations) as well as a thorough analysis of the different contributions to the pNMR shifts. This study paves the way for a more-widespread computational treatment of NMR shifts for paramagnetic materials.

  • 14.
    Nedumkandathil, Reji
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Fischer, Andreas
    Österberg, Carin
    Lin, Yuan-Chih
    Karlsson, Maths
    Grins, Jekabs
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Edén, Mattias
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Häussermann, Ulrich
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Investigation of the Order–Disorder Rotator Phase Transition in KSiH3 and RbSiH32017In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 9, p. 5241-5252Article in journal (Refereed)
    Abstract [en]

    The β–α (order–disorder) transition in the silanides ASiH3 (A = K, Rb) was investigated by multiple techniques, including neutron powder diffraction (NPD, on the corresponding deuterides), Raman spectroscopy, heat capacity (Cp), solid-state 2H NMR spectroscopy, and quasi-elastic neutron scattering (QENS). The crystal structure of α-ASiH3 corresponds to a NaCl-type arrangement of alkali metal ions and randomly oriented, pyramidal, SiH3 moieties. At temperatures below 200 K ASiH3 exist as hydrogen-ordered (β) forms. Upon heating the transition occurs at 279(3) and 300(3) K for RbSiH3 and KSiH3, respectively. The transition is accompanied by a large molar volume increase of about 14%. The Cp(T) behavior is characteristic of a rotator phase transition by increasing anomalously above 120 K and displaying a discontinuous drop at the transition temperature. Pronounced anharmonicity above 200 K, mirroring the breakdown of constraints on SiH3 rotation, is also seen in the evolution of atomic displacement parameters and the broadening and eventual disappearance of libration modes in the Raman spectra. In α-ASiH3, the SiH3 anions undergo rotational diffusion with average relaxation times of 0.2–0.3 ps between successive H jumps. The first-order reconstructive phase transition is characterized by a large hysteresis (20–40 K). 2H NMR revealed that the α-form can coexist, presumably as 2–4 nm (sub-Bragg) sized domains, with the β-phase below the phase transition temperatures established from Cp measurements. The reorientational mobility of H atoms in undercooled α-phase is reduced, with relaxation times on the order of picoseconds. The occurrence of rotator phases α-ASiH3 near room temperature and the presence of dynamical disorder even in the low-temperature β-phases imply that SiH3 ions are only weakly coordinated in an environment of A+ cations. The orientational flexibility of SiH3 can be attributed to the simultaneous presence of a lone pair and (weakly) hydridic hydrogen ligands, leading to an ambidentate coordination behavior toward metal cations.

  • 15.
    Nedumkandathil, Reji
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Grins, Jekabs
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Bernin, Diana
    Karlsson, Maths
    Eklof-Österberg, Carin
    Neagu, Alexandra
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Tai, Cheuk-Wai
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Häussermann, Ulrich
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Hydride Reduction of BaTiO3 - Oxyhydride Versus O Vacancy Formation2018In: Acs Omega, ISSN 2470-1343, Vol. 3, no 9, p. 11426-11438Article in journal (Refereed)
    Abstract [en]

    We investigated the hydride reduction of tetragonal BaTiO3 using the metal hydrides CaH2, NaH, MgH2, NaBH4, and NaAlH4. The reactions employed molar BaTiO3/H ratios of up to 1.8 and temperatures near 600 degrees C. The air-stable reduced products were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy, thermogravimetric analysis (TGA), and H-1 magic angle spinning (MAS) NMR spectroscopy. PXRD showed the formation of cubic products-indicative of the formation of BaTiO3-xHx. except for NaH. Lattice parameters were in a range between 4.005 angstrom (for NaBH4-reduced samples) and 4.033 A (for MgH2-reduced samples). With increasing H/BaTiO3 ratio, CaH2-, NaAlH4-, and MgH2-reduced samples were afforded as two-phase mixtures. TGA in air flow showed significant weight increases of up to 3.5% for reduced BaTiO3, suggesting that metal hydride reduction yielded oxyhydrides BaTiO3-xHx with x values larger than 0.5. H-1 MAS NMR spectroscopy, however, revealed rather low concentrations of H and thus a simultaneous presence of O vacancies in reduced BaTiO3. It has to be concluded that hydride reduction of BaTiO3 yields complex disordered materials BaTiO3-xHy square((x-y)) with x up to 0.6 and y in a range 0.04-0.25, rather than homogeneous solid solutions BaTiO3-xHx. Resonances of (hydridic) H substituting O in the cubic perovskite structure appear in the -2 to -60 ppm spectral region. The large range of negative chemical shifts and breadth of the signals signifies metallic conductivity and structural disorder in BaTiO3-xHy square((x-y)). Sintering of BaTiO3-xHy square((x-y)) in a gaseous H-2 atmosphere resulted in more ordered materials, as indicated by considerably sharper H-1 resonances.

  • 16.
    Nedumkandathil, Reji
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Grins, Jekabs
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Bernin, Diana
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Karlsson, Maths
    Österberg, Carin
    Neagu, Alexandra
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Tai, Cheuk-Wai
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Häussermann, Ulrich
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Hydride Reduction of BaTiO3 – Oxyhydride vs O-Vacancy FormationManuscript (preprint) (Other academic)
    Abstract [en]

    We investigated the hydride reduction of tetragonal BaTiO3 using the metal hydrides CaH2, NaH, MgH2, NaBH4 and NaAlH4. The reactions employed molar BaTiO3:H ratios of up to 1.8 and temperatures near 600 °C. The air stable reduced products were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy, thermogravimetric analysis (TGA) and solid-state 1H NMR spectroscopy. PXRD showed the formation of cubic products - indicative of the formation of BaTiO3-xHx - except for NaH. Lattice parameters were in a range between 4.005 Å (for NaBH4 reduces samples) and 4.033 Å (for MgH2 reduced samples). With increasing BaTiO3:H ratio, CaH2, NaAlH4 and MgH2 reduced samples were afforded as two-phase mixtures. TGA in air flow showed significant weight increase of up to 3.5 % for reduced BaTiO3, suggesting that metal hydride reduction yielded oxyhydrides BaTiO3-xHx with x values larger 0.5. 1H NMR, however, revealed rather low concentrations of H, and, thus a simultaneous presence of O vacancies in reduced BaTiO3. It has to be concluded that hydride reduction of BaTiO3 yields complex disordered materials BaTiO3-xHy(x-y) with x up to 0.6, y in a range 0.05 – 0.2 and (x-y) > y, rather than homogeneous solid solutions BaTiO3Hx. Resonances of (hydridic) H substituting O in the cubic perovskite structure appear in the -2 to -60 ppm spectral region. The large range of chemical shifts and breadth of the signals signifies the structural disorder in BaTiO3-xHy(x-y). Sintering of BaTiO3-xHy(x-y) in a gaseous H2 atmosphere resulted in more ordered materials as indicated by considerably sharper 1H resonances.

  • 17.
    Pell, Andrew J.
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pintacuda, Guido
    Grey, Clare P.
    Paramagnetic NMR in solution and the solid state2019In: Progress in nuclear magnetic resonance spectroscopy, ISSN 0079-6565, E-ISSN 1873-3301, Vol. 111, p. 1-271Article, review/survey (Refereed)
    Abstract [en]

    The field of paramagnetic NMR has expanded considerably in recent years. This review addresses both the theoretical description of paramagnetic NMR, and the way in which it is currently practised. We provide a review of the theory of the NMR parameters of systems in both solution and the solid state. Here we unify the different languages used by the NMR, EPR, quantum chemistry/DFT, and magnetism communities to provide a comprehensive and coherent theoretical description. We cover the theory of the paramagnetic shift and shift anisotropy in solution both in the traditional formalism in terms of the magnetic susceptibility tensor, and using a more modern formalism employing the relevant EPR parameters, such as are used in first-principles calculations. In addition we examine the theory first in the simple non-relativistic picture, and then in the presence of spin-orbit coupling. These ideas are then extended to a description of the paramagnetic shift in periodic solids, where it is necessary to include the bulk magnetic properties, such as magnetic ordering at low temperatures. The description of the paramagnetic shift is completed by describing the current understanding of such shifts due to lanthanide and actinide ions. We then examine the paramagnetic relaxation enhancement, using a simple model employing a phenomenological picture of the electronic relaxation, and again using a more complex state-of-the-art theory which incorporates electronic relaxation explicitly. An additional important consideration in the solid state is the impact of bulk magnetic susceptibility effects on the form of the spectrum, where we include some ideas from the field of classical electrodynamics. We then continue by describing in detail the solution and solid-state NMR methods that have been deployed in the study of paramagnetic systems in chemistry, biology, and the materials sciences. Finally we describe a number of case studies in paramagnetic NMR that have been specifically chosen to highlight how the theory in part one, and the methods in part two, can be used in practice. The systems chosen include small organometallic complexes in solution, solid battery electrode materials, metalloproteins in both solution and the solid state, systems containing lanthanide ions, and multi-component materials used in pharmaceutical controlled-release formulations that have been doped with paramagnetic species to measure the component domain sizes. 

  • 18.
    Pell, Andrew J.
    et al.
    University of Cambridge, United Kingdom.
    Sanders, Kevin J.
    Wegner, Sebastian
    Pintacuda, Guido
    Grey, Clare P.
    Low-power broadband solid-state MAS NMR of 14N2017In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 146, article id 194202Article in journal (Refereed)
  • 19. Pigliapochi, Roberta
    et al.
    O'Brien, Liam
    Pell, Andrew J.
    University of Cambridge, U.K..
    Gaultois, Michael W.
    Janssen, Yuri
    Khalifah, Peter G.
    Grey, Clare P.
    When Do Anisotropic Magnetic Susceptibilities Lead to Large NMR Shifts? Exploring Particle Shape Effects in the Battery Electrode Material LiFePO42019In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 141, no 33, p. 13089-13100Article in journal (Refereed)
  • 20. Pigliapochi, Roberta
    et al.
    Pell, Andrew J.
    University of Cambridge, United Kingdom.
    Seymour, Ieuan D.
    Grey, Clare P.
    Ceresoli, Davide
    Kaupp, Martin
    DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids2017In: Physical Review B. Condensed Matter and Materials Physics, ISSN 1098-0121, E-ISSN 1550-235X, Vol. 95, no 5, article id 054412Article in journal (Refereed)
  • 21. Pigliapochi, Roberta
    et al.
    Seymour, Ieuan D.
    Merlet, Céline
    Pell, Andrew J.
    University of Cambridge, United Kingdom.
    Murphy, Denissa T.
    Schmid, Siegbert
    Grey, Clare P.
    Structural Characterization of the Li-Ion Battery Cathode Materials LiTixMn2–xO4 (0.2 ≤ x ≤ 1.5): A Combined Experimental 7Li NMR and First-Principles Study2018In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 30, no 3, p. 817-829Article in journal (Refereed)
  • 22.
    Rzepka, Przemyslaw
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Bacsik, Zoltan
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Hedin, Niklas
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    The Nature of Chemisorbed CO2 in Zeolite AIn: Article in journal (Refereed)
  • 23.
    Rzepka, Przemyslaw
    et al.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Bacsik, Zoltan
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Hedin, Niklas
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Nature of Chemisorbed CO2 in Zeolite A2019In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 123, no 35, p. 21497-21503Article in journal (Refereed)
    Abstract [en]

    Formation of CO32- and HCO3- species without the participation of the framework-bridging oxygen atoms (-O-) upon chemisorption of CO2 in zeolite vertical bar Na-12 vertical bar-A is revealed. The transfer of O and H atoms is very likely to have proceeded via the involvement of residual H2O or -OH groups. A combined study by the solid-state H-1 and C-13 MAS NMR, quantum chemical calculations, and in situ infrared spectroscopy showed that the chemisorption mainly occurred by the formation of HCO3-. However, at a low surface coverage of physisorbed and acidic CO2, a significant fraction of HCO3- was deprotonated and transformed into CO32-. We expect that a similar chemisorption of CO2 would occur for low-silica zeolites and other basic silicates of interest for capture of CO2 from the gas mixtures.

  • 24. Sanders, Kevin J.
    et al.
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Wegner, Sebastian
    Grey, Clare P.
    Pintacuda, Guido
    Broadband MAS NMR spectroscopy in the low-power limit2018In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 697, p. 29-37Article in journal (Refereed)
    Abstract [en]

    We investigate the performance of broadband adiabatic inversion pulses in the high-power (short high-powered adiabatic pulse, SHAP) and low-power (single-sideband-selective adiabatic pulse, S(3)AP) RF regimes on a spin system subjected to large anisotropic interactions. We show by combined experimental results and spin dynamics simulations that when the magic-angle spinning rate exceeds 100 kHz S(3)APs begin outperforming SHAPs. This is especially true for low-gamma nuclei, such as Li-6 in paramagnetic Li-ion battery materials. Finally, we show how S3APs can be improved by combining multiple waveforms sweeping over multiple sidebands simultaneously, in order to produce inverted sideband profiles free from intensity biasing.

  • 25. Schlagnitweit, Judith
    et al.
    Friebe Sandoz, Sarah
    Jaworski, Aleksander
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Guzzetti, Ileana
    Aussenac, Fabien
    Carbajo, Rodrigo J.
    Chiarparin, Elisabetta
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
    Petzold, Katja
    Observing an Antisense Drug Complex in Intact Human Cells by in-Cell NMR Spectroscopy2019In: ChemBioChem (Print), ISSN 1439-4227, E-ISSN 1439-7633, Vol. 20, p. 2474-2478Article in journal (Refereed)
    Abstract [en]

    Gaining insight into the uptake, trafficking and target engagement of drugs in cells can enhance understanding of a drug's function and efficiency. However, there are currently no reliable methods for studying untagged biomolecules in macromolecular complexes in intact human cells. Here we have studied an antisense oligonucleotide (ASO) drug in HEK 293T and HeLa cells by NMR spectroscopy. Using a combination of transfection, cryoprotection and dynamic nuclear polarization (DNP), we were able to detect the drug directly in intact frozen cells. Activity of the drug was confirmed by quantitative reverse transcription polymerase chain reaction (qRT-PCR). By applying DNP NMR to frozen cells, we overcame limitations both of solution-state in-cell NMR spectroscopy (e.g., size, stability and sensitivity) and of visualization techniques, in which (e.g., fluorescent) tagging of the ASO decreases its activity. The capability to detect an untagged, active drug, interacting in its natural environment, represents a first step towards studying molecular mechanisms in intact cells.

  • 26. Seymour, Ieuan D.
    et al.
    Middlemiss, Derek S.
    Halat, David M.
    Trease, Nicole M.
    Pell, Andrew J.
    Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). University of Cambridge, United Kingdom.
    Grey, Clare P.
    Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via O-17 NMR and DFT Calculations2016In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 138, no 30, p. 9405-9408Article in journal (Refereed)
    Abstract [en]

    Experimental techniques that probe the local environment around O in paramagnetic Li-ion cathode materials are essential in order to understand the complex phase transformations and O redox processes that can occur during electrochemical delithiation. While Li NMR is a well-established technique for studying the local environment of Li ions in paramagnetic battery materials, the use of O-17 NMR in the same materials has not yet been reported. In this work, we present a combined O-17 NMR and hybrid density functional theory study of the local O environments in Li2MnO3, a model compound for layered Li-ion batteries. After a simple O-17 enrichment procedure, we observed five resonances with large O-17 shifts ascribed to the Fermi contact interaction with directly bonded Mn4+ ions. The five peaks were separated into two groups with shifts at 1600 to 1950 ppm and 2100 to 2450 ppm, which, -with the aid of first principles calculations, were assigned to the O-17 shifts of environments similar to the 4i and 8j sites in pristine Li2MnO3, respectively. The multiple O environments in each region were ascribed to the presence of stacking faults within the Li2MnO3 structure. From the ratio of the intensities of the different O-17 environments, the percentage of stacking faults was found to be ca. 10%. The methodology for studying (17)Oshifts in paramagnetic solids described in this work will be useful for studying the local environments of O in a range of technologically interesting transition metal oxides.

  • 27. Tsiamtsouri, Maria A.
    et al.
    Allan, Phoebe K.
    Pell, Andrew J.
    University of Cambridge, United Kingdom.
    Stratford, Joshua M.
    Kim, Gunwoo
    Kerber, Rachel N.
    Magusin, Pieter C. M. M.
    Jefferson, David A.
    Grey, Clare P.
    Exfoliation of Layered Na-Ion Anode Material Na2Ti3O7 for Enhanced Capacity and Cyclability2018In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 30, no 5, p. 1505-1516Article in journal (Refereed)
1 - 27 of 27
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