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1.
J Am Chem Soc ; 145(16): 9081-9091, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37040083

RESUMO

Zeolites are key materials in both basic research and industrial applications. However, their synthesis is neither diverse nor applicable to labile frameworks because classical procedures require harsh hydrothermal conditions, whereas post-synthesis methods are limited to a few suitable parent materials. Remaining frameworks can fail due to amorphization, dissolution, and other decomposition processes. Nevertheless, stopping degradation at intermediate structures could yield new zeolites. Here, by optimizing the design and synthesis parameters of the parent zeolite IWV, we "caught" a new, highly crystalline, and siliceous zeolite during its degradation. IWV seed-assisted crystallization followed by gentle transformation into the water-alcohol system yielded the highly crystalline daughter zeolite IPC-20, whose structure was solved by precession-assisted three-dimensional electron diffraction. Without additional requirements, as in conventional (direct or post-synthesis) strategies, our approach may be applied to any chemically labile material with a staged structure.

2.
Nat Chem ; 15(6): 848-855, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-37081207

RESUMO

Continuous-rotation 3D electron diffraction methods are increasingly popular for the structure analysis of very small organic molecular crystals and crystalline inorganic materials. Dynamical diffraction effects cause non-linear deviations from kinematical intensities that present issues in structure analysis. Here, a method for structure analysis of continuous-rotation 3D electron diffraction data is presented that takes multiple scattering effects into account. Dynamical and kinematical refinements of 12 compounds-ranging from small organic compounds to metal-organic frameworks to inorganic materials-are compared, for which the new approach yields significantly improved models in terms of accuracy and reliability with up to fourfold reduction of the noise level in difference Fourier maps. The intrinsic sensitivity of dynamical diffraction to the absolute structure is also used to assign the handedness of 58 crystals of 9 different chiral compounds, showing that 3D electron diffraction is a reliable tool for the routine determination of absolute structures.

3.
Dalton Trans ; 50(36): 12419-12423, 2021 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-34545879

RESUMO

Intercalation of Cu into layered polychalcogenide La2O2S2 was demonstrated to be viable both under solvothermal conditions at 200 °C and mechanical ball milling at ambient temperature. This result evidences the soft-chemical nature of metal intercalation into layered polychalcogenides driven by the redox reactivity of anion-anion bonds.

4.
Inorg Chem ; 60(20): 15169-15179, 2021 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-34559506

RESUMO

Sedovite, U4+(Mo6+O4)2·nH2O, is reported as being one of the earliest supergene minerals formed of the secondary zone. The difficulty of isolating enough pure material limits studies to techniques that can access the nanoscale combined with theoretical analyses. The crystal structure of sedovite has been solved and refined using the dynamical approach from three-dimensional electron diffraction data collected on natural nanocrystals found among iriginite. At 100 K, sedovite is monoclinic a ≈ 6.96 Å, b ≈ 9.07 Å, c ≈ 12.27 Å, and V ≈ 775 Å3 with space group C2/c. The microporous structure presents a characteristic framework built from uranium polyhedra and disordered Mo pyramids creating pore hosting water molecules. To confirm the formula U4+(Mo6+O4)2·nH2O, the possible presence of a hydroxyl group that would promote Mo5+ was tested with density functional theory (DFT) computations at the ambient temperature. DFT predicts that sedovite is a ferromagnetic insulator with a fundamental bandgap of Eg ∼ 1.7 eV with its chemical and physical properties dominated by U4+ rather than Mo6+. The structural complexity, IG,tot, of sedovite was evaluated in order to get indirect information about the missing formation conditions.

5.
Nat Commun ; 12(1): 3605, 2021 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-34127660

RESUMO

Designing and synthesising new metastable compounds is a major challenge of today's material science. While exploration of metastable oxides has seen decades-long advancement thanks to the topochemical deintercalation of oxygen as recently spotlighted with the discovery of nickelate superconductor, such unique synthetic pathway has not yet been found for chalcogenide compounds. Here we combine an original soft chemistry approach, structure prediction calculations and advanced electron microscopy techniques to demonstrate the topochemical deintercalation/reintercalation of sulfur in a layered oxychalcogenide leading to the design of novel metastable phases. We demonstrate that La2O2S2 may react with monovalent metals to produce sulfur-deintercalated metastable phases La2O2S1.5 and oA-La2O2S whose lamellar structures were predicted thanks to an evolutionary structure-prediction algorithm. This study paves the way to unexplored topochemistry of mobile chalcogen anions.

6.
IUCrJ ; 8(Pt 1): 116-123, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-33520247

RESUMO

Kaatialaite mineral Fe[AsO2(OH)2]5H2O from Jáchymov, Czech Republic forms white aggregates of needle-shaped crystals with micrometric size. Its structure at ambient temperature has already been reported but hydrogen atoms could not be identified from single-crystal X-ray diffraction. An analysis using 3D electron diffraction at low temperature brings to light the hydrogen positions and the existence of hydrogen disorder. At 100 K, kaatialaite is described in a monoclinic unit cell of a = 15.46, b = 19.996, c = 4.808 Å, ß = 91.64° and V = 1485.64 Å3 with space group P21/n. The hydrogen sites were revealed after refinements both considering the dynamical effects and ignoring them. The possibility to access most of the hydrogen positions, including partially occupied ones among heavy atoms, from the kinematical refinement is due to the recent developments in the analysis of 3D electron data. The hydrogen bonding observed in kaatialaite provides examples of H2O configurations that have not been observed before in the structures of oxysalts with the presence of unusual inverse transformer H2O groups.

7.
Angew Chem Int Ed Engl ; 59(50): 22382-22387, 2020 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-32809237

RESUMO

In this work we benefited from recent advances in tools for crystal-structure analysis that enabled us to describe an exotic nanoscale phenomenon in structural chemistry. The Mn0.60 Ni0.40 As sample of the Mn1-x Nix As solid solution, exhibits an incommensurate compositional modulation intimately coupled with positional modulations. The average structure is of the simple NiAs type, but in contrast to a normal solid solution, we observe that manganese and nickel segregate periodically at the nano-level into ordered MnAs and NiAs layers with thickness of 2-4 face-shared octahedra. The detailed description was obtained by combination of 3D electron diffraction, scanning transmission electron microscopy, and neutron diffraction. The distribution of the manganese and nickel layers is perfectly described by a modulation vector q=0.360(3) c*. Displacive modulations are observed for all elements as a consequence of the occupational modulation, and as a means to achieve acceptable Ni-As and Mn-As distances. This modulated evolution of magnetic MnAs and non-magnetic NiAs-layers with periodicity at approximately 10 Šlevel, may provide an avenue for spintronics.

8.
Sci Rep ; 9(1): 9156, 2019 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-31235777

RESUMO

As a metastable phase, vaterite is involved in the first step of crystallization of several carbonate-forming systems including the two stable polymorphs calcite and aragonite. Its complete structural determination would consequently shed important light to understand scaling formation and biomineralization processes. While vaterite's hexagonal substructure (a0 ~ 4.1 Å and c0 ~ 8.5 Å) and the organization of the carbonate groups within a single layer is known, conflicting interpretations regarding the stacking sequence remain and preclude the complete understanding of the structure. To resolve the ambiguities, we performed precession electron diffraction tomography (PEDT) to collect single crystal data from 100 K to the ambient temperature. The structure was solved ab initio and described over all the temperature range using a unified modulated structure model in the superspace group C12/c1(α0γ)00 with a = a0 = 4.086(3) Å, b = [Formula: see text]a0 = 7.089(9) Å, c = c0 = 8.439(9) Å, α = ß = γ = 90° and q = [Formula: see text]a* + γc*. At 100 K the model presents a pure 4-layer stacking sequence with γ = [Formula: see text] whereas at the ambient temperature, ordered stacking faults are introduced leading to γ < [Formula: see text]. The model was refined against PEDT data using the dynamical refinement procedure including modulation and twinning as well as against x-ray powder data by the Rietveld refinement.

9.
RSC Adv ; 9(34): 19657-19661, 2019 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-35519355

RESUMO

The crystal structure of the U(iv)-phosphate mineral vyacheslavite has been solved from precession electron diffraction tomography (PEDT) data from the natural nano-crystal and further refined using density-functional theory (DFT) calculations. Vyacheslavite is orthorhombic, with the space group Cmca, with a ≈ 6.96 Å, b ≈ 9.07 Å and c ≈ 12.27 Å, V ≈ 775 Å3 (obtained from PEDT data at 100 K), Z = 8. Its structure is a complex heteropolyhedral framework consisting of sheets of UO7(OH) and PO4 polyhedra, running parallel to (001), interconnected by additional PO4 polyhedra. There is an (OH) group associated with the U(iv) polyhedron. The question of H2O presence within the small cavities of the framework has been addressed by the DFT calculations, which have proved that vyacheslavite does not contain any significant amount of H2O at room temperature.

10.
Acta Crystallogr B Struct Sci Cryst Eng Mater ; 75(Pt 4): 512-522, 2019 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-32830709

RESUMO

Electron diffraction tomography (EDT) data are in many ways similar to X-ray diffraction data. However, they also present certain specifics. One of the most noteworthy is the specific rocking curve observed for EDT data collected using the precession electron diffraction method. This double-peaked curve (dubbed `the camel') may be described with an approximation based on a circular integral of a pseudo-Voigt function and used for intensity extraction by profile fitting. Another specific aspect of electron diffraction data is the high likelihood of errors in the estimation of the crystal orientation, which may arise from the inaccuracies of the goniometer reading, crystal deformations or crystal movement during the data collection. A method for the refinement of crystal orientation for each frame individually is proposed based on the least-squares optimization of simulated diffraction patterns. This method provides typical angular accuracy of the frame orientations of less than 0.05°. These features were implemented in the computer program PETS 2.0. The implementation of the complete data processing workflow in the program PETS and the incorporation of the features specific for electron diffraction data is also described.

11.
Inorg Chem ; 57(6): 3107-3115, 2018 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-29474066

RESUMO

We report the possibility of extending the so-called stairlike Aurivilius phases in the pseudobinary Bi5Nb3O15-ABi2Nb2O9 (A = Ba and Sr) over a wide range of compositions. These phases are characterized by a discontinuous stacking of [Bi2O2] slabs and perovskite blocks, leading to long-period intergrowths stabilized as a single phase. When analyses from precession electron diffraction tomography and X-ray and neutron powder diffraction are combined, the monoclinic incommensurately modulated structure with q = αa* + γc* previously proposed for the ABi7Nb5O24 composition could be generalized to the Bi5Nb3O15-ABi2Nb2O9 (A = Ba and Sr) compounds. Considering the compositions expressed as (A,Bi)1- xNb xO3-3 x, the stacking sequence associated with compositions ranging from x = 2/5 to 3/8 is governed by the component γ of the modulation vector and can be predicted following a Farey tree hierarchy independently to the A cation. The length of the steps, characteristic of the stairlike nature, is controlled by the α component and depends on the substitution ratio A/Bi and the nature of A (A = Ba and Sr). This study highlights the compositional flexibility of stairlike Aurivillius phases.

12.
Nano Lett ; 17(11): 6575-6582, 2017 11 08.
Artigo em Inglês | MEDLINE | ID: mdl-28968496

RESUMO

Layered materials, e.g., graphene and transition metal (di)chalcogenides, holding great promises in nanoscale device applications have been extensively studied in fundamental chemistry, solid state physics and materials research areas. In parallel, layered oxides (e.g., Aurivillius and Ruddlesden-Popper phases) present an attractive class of materials both because of their rich physics behind and potential device applications. In this work, we report a novel layered oxide material with self-assembled layered supercell structure consisting of two mismatch-layered sublattices of [Bi3O3+δ] and [MO2]1.84 (M = Al/Mn, simply named BAMO), i.e., alternative layered stacking of two mutually incommensurate sublattices made of a three-layer-thick Bi-O slab and a one-layer-thick Al/Mn-O octahedra slab in the out-of-plane direction. Strong room-temperature ferromagnetic and piezoelectric responses as well as anisotropic optical property have been demonstrated with great potentials in various device applications. The realization of the novel BAMO layered supercell structure in this work has paved an avenue toward exploring and designing new materials with multifunctionalities.

13.
Adv Mater ; 29(22)2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-28370578

RESUMO

Transition metal oxides having a perovskite structure form a wide and technologically important class of compounds. In these systems, ferroelectric, ferromagnetic, ferroelastic, or even orbital and charge orderings can develop and eventually coexist. These orderings can be tuned by external electric, magnetic, or stress field, and the cross-couplings between them enable important multifunctional properties, such as piezoelectricity, magneto-electricity, or magneto-elasticity. Recently, it has been proposed that additional to typical fields, the chemical potential that controls the concentration of ion vacancies in these systems may reveal an efficient alternative parameter to further tune their properties and achieve new functionalities. In this study, concretizing this proposal, the authors show that the control of the content of oxygen vacancies in perovskite thin films can indeed be used to tune their magnetic properties. Growing PrVO3 thin films epitaxially on an SrTiO3 substrate, the authors reveal a concrete pathway to achieve this effect. The authors demonstrate that monitoring the concentration of oxygen vacancies through the oxygen partial pressure or the growth temperature can produce a substantial macroscopic tensile strain of a few percent. In turn, this strain affects the exchange interactions, producing a nontrivial evolution of Néel temperature in a range of 30 K.

14.
Inorg Chem ; 55(17): 8881-91, 2016 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-27525499

RESUMO

New ferroelectric layered materials were found in the pseudobinary system Bi5Nb3O15-ABi2Nb2O9 (A= Ba, Sr and Pb). Preliminary observations made by transmission electron microscopy indicate that these compounds exhibit a complex incommensurately modulated structure. A (3 + 1)D structural model is obtained using ab initio phasing by charge flipping based on the analysis of precession electron diffraction tomography data. The (3 + 1)D structure is further validated by a refinement against neutron powder diffraction. These materials possess a layered structure with discontinuous [Bi2O2] slabs and perovskite blocks. While these structural units are characteristics of Aurivillius phases, the existence of periodic crystallographic shear planes offers strong similarities with collapsed or stairlike structures known in high-Tc superconductors and related compounds. Using dielectric spectroscopy, we study the phase transitions of these new layered materials. For A = Ba and Sr, a Vögel-Fulcher-like behavior characteristic of the so-called relaxor ferroelectrics is observed and compared to "canonical" relaxors. For A = Sr, the absence of a Burns temperature separated from the freezing temperature appears as a rather unusual behavior.

15.
Acta Crystallogr B Struct Sci Cryst Eng Mater ; 71(Pt 6): 740-51, 2015 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-26634732

RESUMO

The recently published method for the structure refinement from three-dimensional precession electron diffraction data using dynamical diffraction theory [Palatinus et al. (2015). Acta Cryst. A71, 235-244] has been applied to a set of experimental data sets from five different samples - Ni2Si, PrVO3, kaolinite, orthopyroxene and mayenite. The data were measured on different instruments and with variable precession angles. For each sample a reliable reference structure was available. A large series of tests revealed that the method provides structure models with an average error in atomic positions typically between 0.01 and 0.02 Å. The obtained structure models are significantly more accurate than models obtained by refinement using kinematical approximation for the calculation of model intensities. The method also allows a reliable determination of site occupancies and determination of absolute structure. Based on the extensive tests, an optimal set of the parameters for the method is proposed.

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