Bismuth-Catalyzed Growth of SnS2 Nanotubes and Their Stability

"Ab initio" structure solution from electron diffraction data obtained by a combination of automated diffraction tomography and precession technique

Using a combination of our recently developed automated diffraction tomography (ADT) module with precession electron technique (PED), quasi-kinematical 3D diffraction data sets of an inorganic salt (BaSO(4)) were collected. The lattice cell parameters and their orientation within the data sets were found automatically. The extracted intensities were used for "ab initio" structure analysis by direct methods. The data set covered almost the complete set of possible symmetrically equivalent reflections for an orthorhombic structure. The structure solution in one step delivered all heavy (Ba, S) as well as light atoms (O). Results of the structure solution using direct methods, charge flipping …

A new hydrous Al-bearing pyroxene as a water carrier in subduction zones

Abstract A new Hydrous Al-bearing PYroxene (HAPY) phase has been synthesized at 5.4 GPa, 720 °C in the MgO–Al2O3–SiO2–H2O model system. It has the composition Mg2.1Al0.9(OH)2Al0.9Si1.1O6, a C-centered monoclinic cell with a = 9.8827(2), b = 11.6254(2) c = 5.0828(1) A and β = 111.07(1)°. The calculated density is 3.175 g/cm3 and the water content is 6.9% H2O by weight. Its structure has been solved in space group C2/c by the recently developed automated electron diffraction tomography method and refined by synchrotron X-ray powder diffraction. HAPY is a single chain inosilicate very similar to pyroxenes but with three instead of two cations in the octahedral layer, bonded to four oxygens and…

Automated Diffraction Tomography: A New Era for Electron Crystallography

Extended abstract of a paper presented at Microscopy and Microanalysis 2011 in Nashville, Tennessee, USA, August 7–August 11, 2011.

Ab Initio Structure Determination of Vaterite by Automated Electron Diffraction

tion that is fundamental for understanding material properties. Still, a number of compounds have eluded such kinds of analysis because they are nanocrystalline, highly disordered, with strong pseudosymmetries or available only in small amounts in polyphasic or polymorphic systems. These materials are crystallographically intractable with conventional Xray or synchrotron radiation diffraction techniques. Single nanoparticles can be visualized by high-resolution transmission electron microscopy (HR-TEM) up to sub�ngstrom resolution, [2] but obtaining 3D information is still a difficult task, especially for highly beam-sensitive materials and crystal structures with long cell parameters. Elec…

Crystalline nanorods as possible templates for the synthesis of amorphous biosilica during spicule formation in Demospongiae.

In tandem: High-resolution TEM shows that during the initial stages of demosponge spicule formation, a primordial crystalline structure is formed within the axial filament. The recently developed electron diffraction tomography technique (ADT) reveals that the nanorods have a layered structure that matches smectitic phyllosilicates. These intracellular nanorods have been considered as precursors of mature spicules. High-resolution microscopy shows that, during the initial stages of demosponge spicule formation, a primordial crystalline structure is formed within the axial filament. The recently developed electron diffraction tomography technique reveals that the nanorods have a layered stru…

Biosilicification of loricate choanoflagellate: organic composition of the nanotubular siliceous costal strips of Stephanoeca diplocostata.

SUMMARY Loricate choanoflagellates (unicellular, eukaryotic flagellates; phylum Choanozoa) synthesize a basket-like siliceous lorica reinforced by costal strips (diameter of approximately 100 nm and length of 3 μm). In the present study, the composition of these siliceous costal strips is described, using Stephanoeca diplocostata as a model. Analyses by energy-dispersive X-ray spectroscopy (EDX), coupled with transmission electron microscopy (TEM), indicate that the costal strips comprise inorganic and organic components. The organic, proteinaceous scaffold contained one major polypeptide of mass 14 kDa that reacted with wheat germ agglutinin. Polyclonal antibodies were raised that allowed …

Facile hydrothermal synthesis of crystalline Ta2O5 nanorods, MTaO3 (M = H, Na, K, Rb) nanoparticles, and their photocatalytic behaviour

Alkali metal tantalates are of interest for applications in photocatalysis as well as in high temperature resistance or capacitor dielectric materials. We have synthesized nanosized Ta2O5 rods and MTaO3 cubes (M = Na, K, Rb) hydrothermally and demonstrate the pH dependence of the synthesis of tantalum oxide and tantalate nanoparticles. The morphologies of the nanoparticles range from particle agglomerates in acidic reaction media over rods at neutral pH to tantalate cubes in basic reaction media. Whereas there is no apparent influence of the base cation on the particle morphology, there is a pronounced effect on the particle composition. At high base concentrations cubic tantalate particles…

Synthesis of a quenchable high-pressure form of magnetite (h-Fe3O4) with composition Fe1(Fe2+0.75Mg0.26)Fe2(Fe3+0.70Cr0.15Al0.11Si0.04)2O4

We report the synthesis of h-magnetite, ideally h-Fe 3 O 4 with considerable amounts of substitutional cations (Cr, Mg, Al, Si) and quenchable to ambient conditions. Two types of experiments were performed at 18 GPa and 1800 °C in a multi-anvil press. In one, we used an oxide mixture with a majoritic stoichiometry Mg 1.8 Fe 1.2 (Al 1.4 Cr 0.2 Si 0.2 Mg 0.2 )Si 3 O 12 , with Si and Mg in excess as starting material (MA-367, MA-380). In the second type of experiment (MA-376), we started from an oxide mixture on the composition of the Fe-oxide phase obtained in MA-367. The Fe-oxide phases of both experiments were investigated by electron microprobe and transmission electron microscopy includin…

Elucidating Gating Effects for Hydrogen Sorption in MFU-4-Type Triazolate-Based Metal-Organic Frameworks Featuring Different Pore Sizes

A highly porous member of isoreticular MFU-4-type frameworks, [Zn(5)Cl(4)(BTDD)(3)] (MFU-4l(arge)) (H(2)-BTDD=bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), has been synthesized using ZnCl(2) and H(2)-BTDD in N,N-dimethylformamide as a solvent. MFU-4l represents the first example of MFU-4-type frameworks featuring large pore apertures of 9.1 Å. Here, MFU-4l serves as a reference compound to evaluate the origin of unique and specific gas-sorption properties of MFU-4, reported previously. The latter framework features narrow-sized pores of 2.5 Å that allow passage of sufficiently small molecules only (such as hydrogen or water), whereas molecules with larger kinetic diameters (e.…

Structural insights into M2O-Al2O3-WO3 (M = Na, K) system by electron diffraction tomography.

TheM2O–Al2O3–WO3(M= alkaline metals) system has attracted the attention of the scientific community because some of its members showed potential applications as single crystalline media for tunable solid-state lasers. These materials behave as promising laser host materials due to their high and continuous transparency in the wide range of the near-IR region. A systematic investigation of these phases is nonetheless hampered because it is impossible to produce large crystals and only in a few cases a pure synthetic product can be achieved. Despite substantial advances in X-ray powder diffraction methods, structure investigation on nanoscale is still challenging, especially when the sample i…

Automated electron diffraction tomography - a new tool for nano crystal structure analysis

Automated electron Diffraction Tomography (ADT) comprises an upcoming method for “ab intio” structure analysis of nano crystals. ADT allows fine sampling of the reciprocal space by sequential collection of electron diffraction patterns while tilting a nano crystal in fixed tilt steps around an arbitrary axis. Electron diffraction is collected in nano diffraction mode (NED) with a semi-parallel beam with a diameter down to 50 nm. For crystal tracking micro-probe STEM imaging is used. Full automation of the acquisition procedure allowed optimisation of the electron dose distribution and therefore analysis of highly beam sensitive samples. Cell parameters, space group and reflection intensitie…

Atomic structure solution of the complex quasicrystal approximant Al77Rh15Ru8 from electron diffraction data

The crystal structure of the novel Al77Rh15Ru8phase (which is an approximant of decagonal quasicrystals) was determined using modern direct methods (MDM) applied to automated electron diffraction tomography (ADT) data. The Al77Rh15Ru8E-phase is orthorhombic [Pbma,a= 23.40 (5),b= 16.20 (4) andc= 20.00 (5) Å] and has one of the most complicated intermetallic structures solved solely by electron diffraction methods. Its structural model consists of 78 unique atomic positions in the unit cell (19 Rh/Ru and 59 Al). Precession electron diffraction (PED) patterns and high-resolution electron microscopy (HRTEM) images were used for the validation of the proposed atomic model. The structure of the E…

Morphology of Sponge Spicules: Silicatein a Structural Protein for Bio-Silica Formation

Most forms of multicellular life have developed a calcium-based skeleton, while only a few specialized organisms complement their body plan with silica, such as sponges (phylum Porifera). However, the way in which sponges synthesize their silica is exceptional. They use an enzyme, silicatein, for the polymerization/polycondensation of silica, and thereby form their highly resistant and stabile massive siliceous skeletal elements (spicules). During this biomineralization process (i.e., biosilicification), hydrated amorphous silica is deposited within highly specialized sponge cells, ultimately resulting in structures that range in size from micrometers to meters. This peculiar phenomenon has…

Solution Synthesis of a New Thermoelectric Zn1-xSb Nanophase and Its Structure Determination Using Automated Electron Diffraction Tomography

Engineering materials with specific physical properties have recently focused on the effect of nanoscopic inhomogeneities at the 10 nm scale. Such features are expected to scatter medium- and long-wavelength phonons thereby lowering the thermal conductivity of the system. Low thermal conductivity is a prerequisite for effective thermoelectric materials, and the challenge is to limit the transport of heat by phonons, without simultaneously decreasing charge transport. A solution-phase technique was devised for synthesis of thermoelectric "Zn(4)Sb(3)" nanocrystals as a precursor for phase segregation into ZnSb and a new Zn-Sb intermetallic phase, Zn(1+delta)Sb, in a peritectoid reaction. Our …

Low melting Metal Catalysed Growth of Tin Disulfide Nanotubes

AbstractWe report here the synthesis of tin disulfide nanotubes by a vapour liquid solid growth using bismuth, a low melting metal, as a catalyst. The reaction was carried out in a single step process by heating SnS2 and bismuth in a horizontal tube furnace at 800oC. TEM analysis allowed proposing a plausible mechanism for the formation of SnS2 nanotubes. Pure material could be obtained by optimizing the reaction based on a product analysis using powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) combined with energy dispersive X-ray spectroscopy (EDX).

Iron-clay interactions: Detailed study of the mineralogical transformation of claystone with emphasis on the formation of iron-rich T-O phyllosilicates in a step-by-step cooling experiment from 90 degrees C to 40 degrees C

International audience; Iron-minerals-water interactions are of primary importance in the contexts of underground structure engineering (e.g. reactive barriers or deep geological storage) and for the understanding of secondary alteration processes in primitive meteorites. To improve our understanding of these systems, we determine the mineralogical transformations induced by the association of iron and silicates during a cooling through an experimental simulation of iron-clay interactions with a step-by-step procedure in the range of 90 degrees C to 40 degrees C. The run products and solutions are well characterised, by means of different techniques (X-ray diffraction, scanning and transmis…

Structure characterization of hard materials by precession electron diffraction and automatic diffraction tomography: 6H-SiC semiconductor and Ni1+xTe1 embedded nanodomains

Using a combination of automated diffraction tomography and precession electron diffraction techniques, quasi-kinematical electron diffraction data sets were collected from intermetallic Ni1+xTe1 embedded nanodomains and ion-thinned specimens of 6H–SiC semiconductor. Cell parameters and space groups were found automatically from the reconstructed 3D diffraction volume. The extracted intensities were used for fast ab initio structure determination by direct methods.

Structure analysis of titanate nanorods by automated electron diffraction tomography

A hitherto unknown phase of sodium titanate, NaTi3O6(OH)·2H2O, was identified as the intermediate species in the synthesis of TiO2 nanorods. This new phase, prepared as nanorods, was investigated by electron diffraction, X-ray powder diffraction, thermogravimetric analysis and high-resolution transmission electron microscopy. The structure was determined ab initio using electron diffraction data collected by the recently developed automated diffraction tomography technique. NaTi3O6(OH)·2H2O crystallizes in the monoclinic space group C2/m. Corrugated layers of corner- and edge-sharing distorted TiO6 octahedra are intercalated with Na+ and water of crystallization. The nanorods are typically …

Asymmetric tungsten oxide nanobrushes via oriented attachment and Ostwald ripening

Tungsten oxide nanobrushes were synthesized using a solvothermal approach that lead to self-branching in the presence of citric acid and hexadecylamine as surfactants. Our synthetic approach yielded branched nanorods of tungsten oxide in a single synthetic step. Based on our results, we propose a phenomenological pathway for the formation, branching, and assembly of these tungsten oxide brushes. The formation of tungsten oxide brushes proceeds by thermal decomposition of ammonium tungstate in the presence of citric acid and hexadecylamine. The pale blue powder obtained after solvothermal reaction was analyzed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and high-resolu…

Charoite, as an example of a structure with natural nanotubes

Charoite from the Murun massif in Yakutiya, Russia (Vorob’ev 2008) was investigated using automated electron diffraction tomography (ADT) (Kolb et al. 2007, 2008; Mugnaioli et al. 2010) and precession electron diffraction (PED) (Mugnaioli et al. 2010, 2009), which allowed to determine the structure of charoite for the first time. The structure was solved ab initio in space group P21/m by direct methods using a fully kinematic approach. The least squares refinements with 2878 reflections F(hkl) >4s F converged to unweighted/weighted residuals R 1/wR 2 • 0.173/0.21 (Rozhdestvenskaya et al. 2010).

Enzyme-Mediated Deposition of a TiO2Coating onto Biofunctionalized WS2 Chalcogenide Nanotubes

A chemically specific and facile method for the biofunctionalization of WS2 nanotubes (NT-WS2) is reported. The covalent modification strategy is based on the affinity of the nitrilotriacetic acid (NTA) side chain, which serves as a ligand for the surface binding to NT-WS2 and simultaneously as an anchor group for the binding of His-tagged proteins to the polymer backbone. The polymer functionalized WS2 nanotubes can be solubilized either in water or organic solvents; they are stable for at least one week. The probes were characterized by FT-IR and UV-vis spectroscopy. The immobilization of silicatein, a hydrolytic protein encountered in marine sponges, was visualized by scanning force micr…

Structural Characterisation of Complex Layered Double Hydroxides and TGA-GC-MS Study on Thermal Response and Carbonate Contamination in Nitrate- and Organic-Exchanged Hydrotalcites

Layered double hydroxides (LDHs) are versatile materials used for intercalating bioactive molecules in the fields of pharmaceuticals, nutraceuticals and cosmetics, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability and improving their pharmacokinetic properties and formulation stability. Moreover, LDHs are used in various technological applications to improve stability and processability. The crystal chemistry of hydrotalcite-like compounds was investigated by X-ray powder diffraction (XRPD), automated electron diffraction tomography (ADT) and thermogravimetric analysis (TGA)-GC-MS to shed light on the mechanisms involved in io…

Electron Diffraction Reinvestigation of CdCr<sub>2</sub>Se<sub>4</sub> and ZnCr<sub>2-x</sub>V<sub>x</sub>Se<sub>4</sub> Spinel Structures

Crystal structure of two spinel single crystals CdCr2Se4 and ZnCr2-xVxSe4 have been reinvestigated using automated electron diffraction tomography method with beam precession. 3D reciprocal space have been reconstructed base on recorded tilt series. For both samples crystal structure was refined and the cubic symmetry with space group Fd-3m was confirmed. No additional electron potential has been located beside occupied atom sites.

Assembly and Separation of Semiconductor Quantum Dot Dimers and Trimers

Repeated precipitation of colloidal semiconductor quantum dots (QD) from a good solvent by adding a poor solvent leads to an increasing number of QD oligomers after redispersion in the good solvent. By using density gradient ultracentrifugation we have been able to separate QD monomer, dimer, and trimer fractions from higher oligomers in such solutions. In the corresponding fractions QD dimers and trimers have been enriched up to 90% and 64%, respectively. Besides directly coupled oligomers, QD dimers and trimers were also assembled by linkage with a rigid terrylene diimide dye (TDI) and separated again by ultracentrifugation. High-resolution transmission electron micrographs show that the …

Accurate and precise lattice parameters by selected-area electron diffraction in the transmission electron microscope

8 páginas, 6 figuras, 7 tablas.

Synthesis and Structure Determination of the Hierarchical Meso-Microporous Zeolite ITQ-43

[EN] The formation of mesopores in microporous zeolites is generally performed by postsynthesis acid, basic, and steam treatments. The hierarchical pore systems thus formed allow better adsorption, diffusion, and reactivity of these materials. By combining organic and inorganic structure-directing agents and high-throughput methodologies, we were able to synthesize a zeolite with a hierarchical system of micropores and mesopores, with channel openings delimited by 28 tetrahedral atoms. Its complex crystalline structure was solved with the use of automated diffraction tomography.

Ab-initio-Strukturbestimmung von Vaterit mit automatischer Beugungstomographie

Structural Characterization of Organics Using Manual and Automated Electron Diffraction

In the last decade the importance of transmission electron microscopic studies has become increasingly important with respect to the characterization of organic materials, ranging from small organic molecules to polymers and biological macromolecules. This review will focus on the use of transmission electron microscope to perform electron crystallography experiments, detailing the approaches in acquiring electron crystallographic data. The traditional selected area approach and the recently developed method of automated diffraction tomography (ADT) will be discussed with special attention paid to the handling of electron beam sensitive organic materials.

Automated Diffraction Tomography for the Structure Elucidation of Twinned, Sub-micrometer Crystals of a Highly Porous, Catalytically Active Bismuth Metal-Organic Framework

A multi-technique, micrometer- to atomic-scale description of a synthetic analogue of chukanovite, Fe-2(CO3)(OH)(2)

International audience; A synthetic analogue of chukanovite Fe-2(CO3)(OH)(2) is formed during experimental work on iron-clay interactions simulating the cooling of containers in radioactive waste repositories. Despite its small size and the mixture with other minerals it is undoubtedly identified by X-Ray Diffraction, Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy and Transmission Electron Microscopy. For the first time, the structural characterisation of a synthetic chukanovite is carried out thanks to the combination of Automated Diffraction Tomography and Precession Electron Diffraction. Refinement results and comparison with literature data show that the structure…

ECS-3: A Crystalline Hybrid Organic-Inorganic Aluminosilicate with Open Porosity

Structure analysis on the nanoscale: closed WS2 nanoboxes through a cascade of topo- and epitactic processes

Closed WS2 nanoboxes were formed by topotactic sulfidization of a WO3/WO3·⅓H2O intergrowth precursor. Automated diffraction tomography was used to elucidate the growth mechanism of these unconventional hollow structures. By partial conversion and structural analysis of the products, each of them representing a snapshot of the reaction at a given point in time, the overall reaction can be broken down into a cascade of individual steps and each of them identified with a basic mechanism. During the initial step of sulfidization WO3·⅓H2O transforms into hexagonal WO3 whose surface allows for the epitaxial induction of WS2. The initially formed platelets of WS2 exhibit a preferred orientation wi…

Bismut-katalysiertes Wachstum von SnS2-Nanoröhren und deren Stabilität

A multi-technique characterisation of cronstedtite synthetized by iron-clay interaction in a step by step cooling procedure

International audience; The cooling of steel containers in radioactive-waste storage was simulated in a step-by-step experiment from 90 to 40 degrees C. Among newly formed clay minerals observed in run products, cronstedtite was identified by a number of analytical techniques (powder X-ray diffraction, transmission electron microscopy, and scanning electron microscopy). Cronstedtite has not previously been recognized to be so abundant and so well crystallized in an iron-clay interaction experiment. The supersaturation of experimental solutions with respect to cronstedtite was due to the availability of Fe and Si in solution, as a result of the dissolution of iron metal powder, quartz, and m…

High-Pressure Synthesis of Novel Boron Oxynitride B6N4O3 with Sphalerite Type Structure

A novel crystalline boron oxynitride (BON) phase has been synthesized under static pressures exceeding 15 GPa and temperatures above 1900 °C, from molar mixtures of B2O3 and h-BN. The structure and composition of the synthesized product were studied using high-resolution transmission electron microscopy, electron diffraction, automated diffraction tomography, energy dispersive X-ray spectroscopy and electron energy-loss spectroscopy (EELS). BON shows a hexagonal cell (R3m, Z = 3) with lattice parameters a = 2.55(5) A and c = 6.37(13) A, and a crystal structure closely related to the cubic sphalerite type. The EELS quantification yielded 42 at % B, 35 at % N, and 23 at % O (B:N:O ≈ 6:4:3). E…

Synthesis of Hierarchically Grown ZnO@NT-WS2 Nanocomposites

A chemically specific and facile method for growth of ZnO nanorods on WS2 nanotubes (NT-WS2) is reported. The modification strategy is based on the chalcophilic affinity of Zn, which serves as an anchor to immobilize ZnO colloids onto the WS2 nanotubes. The surface bound ZnO colloids have been used as a seed to grow ZnO nanorods on WS2 nanotubes. The immobilization of ZnO colloids was monitored by UV−vis spectroscopy and photoluminescence spectroscopy whereas the growth of ZnO nanorods was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

MZ-35, a new layered pentasil borosilicate synthesized in the presence of large alkali cations

Abstract A new layered borosilicate has been synthesized in the presence of cesium and sodium cations and its structure has been solved by a combination of automated diffraction tomography (ADT) and X-ray powder diffraction (XRPD). MZ-35 has a composition NaCs 2 [BSi 7 O 16 (OH) 2 ](OH) 2 ·4H 2 O and features space group P-4m2. The unusually small unit cell ( a 7.3081 A, c 10.7520 A) is shared by two random-stacked configurations of the structure: a network of connected pentasil units related to the layer of RUB-18 and a bidimensional checkerboard of intersecting ladders of 4-membered rings. The two configurations are related by the simple face-sharing inversion of a hydroxyl-bearing tetrah…

Hierachical Ni@Fe2O3superparticles through epitaxial growth of γ-Fe2O3nanorods on: In situ formed Ni nanoplates

One endeavour of nanochemistry is the bottom-up synthesis of functional mesoscale structures from basic building blocks. We report a one-pot wet chemical synthesis of Ni@γ-Fe2O3 superparticles containing Ni cores densely covered with highly oriented γ-Fe2O3 (maghemite) nanorods (NRs) by controlled reduction/decomposition of nickel acetate (Ni(ac)2) and Fe(CO)5. Automated diffraction tomography (ADT) of the Ni-Fe2O3 interface in combination with Mossbauer spectroscopy showed that selective and oriented growth of the γ-Fe2O3 nanorods on the Ni core is facilitated through the formation of a Fe0.05Ni0.95 alloy and the appearance of superstructure features that may reduce strain at the Ni-Fe2O3 …

Applications of automated diffraction tomography (ADT) on nanocrystalline porous materials

Abstract Many porous materials, both inorganic and hybrid organic–inorganic, can only be synthesized as nanocrystals. X-ray powder diffraction delivers one-dimensional data from the overall sample and is therefore often limited by peak overlap at low or medium resolution and by peak broadening. Thus, structure solution of materials with large unit cells and low symmetry, disorder or pseudosymmetry, or available only in polyphasic systems, turns out to be problematic or even impossible. Electron diffraction allows collecting three-dimensional structure information from nanocrystalline materials, but is traditionally biased by low completeness of the diffraction data, dynamical scattering and…

“Ab-initio” structure solution of nano-crystalline minerals and synthetic materials by automated electron tomography

Most of the newly discovered mineral phases, as well as many new synthesized industrial materials, appear only in the form of nano crystals, with a size not sufficient for single-crystal x-ray structure analysis. The development of techniques able to investigate the structure of nano crystalline materials is therefore one of the most important frontiers of crystallography. The most widespread technique providing relatively fast and well consolidated routes for structure analysis of bulk materials is x-ray powder diffraction (XRPD). Nevertheless, XRPD suffers from intrinsic 1-dimension reduction of information that greatly limits its applicability in presence of peak broadening and overlappi…

Electron diffraction, X-ray powder diffraction and pair-distribution-function analyses to determine the crystal structures of Pigment Yellow 213, C23H21N5O9.

The crystal structure of the nanocrystalline alpha phase of Pigment Yellow 213 (P.Y. 213) was solved by a combination of single-crystal electron diffraction and X-ray powder diffraction, despite the poor crystallinity of the material. The molecules form an efficient dense packing, which explains the observed insolubility and weather fastness of the pigment. The pair-distribution function (PDF) of the alpha phase is consistent with the determined crystal structure. The beta phase of P.Y. 213 shows even lower crystal quality, so extracting any structural information directly from the diffraction data is not possible. PDF analysis indicates the beta phase to have a columnar structure with a si…

Ba 6 P 12 N 17 O 9 Br 3 – A Column‐Type Phosphate Structure Solved from Single‐Nanocrystal Data Obtained by Automated Electron Diffraction Tomography

Oxonitridophosphate Ba6P12N17O9Br3 was synthesized by heating a multicomponent mixture of BaBr2, BaS, phosphoryl triamide and thiophosphoryl triamide in an evacuated and sealed silica-glass ampoule to 750 °C. Ba6P12N17O9Br3 was obtained as the main product as a nanocrystalline powder. The crystal structure was determined ab initio on the basis of electron diffraction data acquired from a single needle-shaped nanocrystal by automated diffraction tomography. Ba6P12N17O9Br3 crystallizes in the hexagonal space group P63/m (no. 176) with unit cell parameters a = 14.654(19), c = 8.255(9) A and Z = 2. Its structure includes triangular, column-shaped anions of ∞1{(P12N17O9)9–}, which are built from…

Mechanische Spannung und Valenzabsättigung in Konkurrenz: Nano-Münzrollen aus Stapeln nanoskaliger Schichten

3D Electron Diffraction: The Nanocrystallography Revolution

Crystallography of nanocrystalline materials has witnessed a true revolution in the past 10 years, thanks to the introduction of protocols for 3D acquisition and analysis of electron diffraction data. This method provides single-crystal data of structure solution and refinement quality, allowing the atomic structure determination of those materials that remained hitherto unknown because of their limited crystallinity. Several experimental protocols exist, which share the common idea of sampling a sequence of diffraction patterns while the crystal is tilted around a noncrystallographic axis, namely, the goniometer axis of the transmission electron microscope sample stage. This Outlook review…

Advances in automated diffraction tomography

Crystal structure solution by means of electron diffraction or investigation of special structural features needs high quality data acquisition followed by data processing which delivers cell parameters, space group and in the end a 3D data set. The final step is the structure analysis itself including structure solution and subsequent refinement.

Snapshots of the Formation of NaTi3O6(OH)·2H2O Nanowires: A Time-Resolved XRD/HRTEM Study

Layered titanates are important intermediates during the formation of TiO2-related nanostructures in hot concentrated base solution. Microwave-assisted hydrothermal techniques allow a time-resolved ex-situ analysis of the reaction in one-minute intervals by rapid heating and quenching followed by separation and structure analysis of the intermediates. By a combination of powder X-ray diffraction, high resolution electron microscopy (HRTEM), and selected area electron diffraction (SAED) the individual stages of the reaction could be identified. Sodium titanate nanosheets are formed within several minutes by digesting the crystalline TiO2-P25 precursor in NaOH. These nanosheets with a low sod…

Interaction of Alkaline Metal Cations with Oxidic Surfaces: Effect on the Morphology of SnO2 Nanoparticles

Reaction pathways to SnO(2) nanomaterials through the hydrolysis of hydrated tin tetrachloride precursors were investigated. The products were prepared solvothermally starting from hydrated tin tetrachloride and various (e.g., alkali) hydroxides. The influence of the precursor base on the final morphology of the nanomaterials was studied. X-ray powder diffraction (XRD) data indicated the formation of rutile-type SnO(2). Transmission electron microscopy (TEM) studies revealed different morphologies that were formed with different precursor base cations. Data from molecular dynamics (MD) simulations provide theoretical evidence that the adsorption of the cations of the precursor base to the f…

The Bi sulfates from the Alfenza Mine, Crodo, Italy: An automatic electron diffraction tomography (ADT) study

We report about three bismuth sulfates from mineralized quartz dikes from Alfenza (Crodo, Italy), two new phases and a rare mineral, cannonite, all growing on bismuthinite. The first new phase occurs as white, "hortensia-like" aggregates of pseudo-hexagonal platelets, with perfect basal cleavage, similar to 20 mu m wide and few micrometers thick. The approximate composition is Bi2O2(SO4), and cell parameters and symmetry, as determined by automatic diffraction tomography, are a = 22.0(4), b = 16.7(3), c = 15.9(3) angstrom, beta = 102.9(5)degrees, space group Pc or P2/c. A major stacking disorder is detected by HR-SEM images and electron diffraction data.The second new phase was detected onl…

SrP3N5O: a highly condensed layer phosphate structure solved from a nanocrystal by automated electron diffraction tomography.

The oxonitridophosphate SrP(3)N(5)O has been synthesized by heating a multicomponent reactant mixture that consisted of phosphoryl triamide OP(NH(2))(3), thiophosphoryl triamide SP(NH(2))(3), SrS, and NH(4)Cl enclosed in evacuated and sealed silica-glass ampoules up to 750 °C. The compound was obtained as nanocrystalline powder with needle-shaped crystallites. The crystal structure was solved ab initio on the basis of electron diffraction data by means of automated electron diffraction tomography (ADT) and verified by Rietveld refinement with X-ray powder diffraction data. SrP(3)N(5)O crystallizes in the orthorhombic space group Pnma (no. 62) with unit-cell data of a=18.331(2), b=8.086(1), …

The structure of charoite, (K,Sr,Ba,Mn)(15-16)(Ca,Na)(32)[(Si-70(O,OH)(180))](OH,F)(4.0)center dot nH(2)O, solved by conventional and automated electron diffraction

AbstractCharoite, ideally (K,Sr,Ba,Mn)15–16(Ca,Na)32[(Si70(O,OH)180)](OH,F)4.0·nH2O, a rare mineral from the Murun massif in Yakutiya, Russia, was studied using high-resolution transmission electron microscopy, selected-area electron diffraction, X-ray spectroscopy, precession electron diffraction and the newly developed technique of automated electron-diffraction tomography. The structure of charoite (a= 31.96(6) Å,b= 19.64(4) Å,c= 7.09(1) Å, β = 90.0(1)°,V= 4450(24) Å3, space groupP21/m) was solvedab initioby direct methods from 2878 unique observed reflections and refined toR1/wR2= 0.17/0.21. The structure can be visualized as being composed of three different dreier silicate chains: a d…

Using FOCUS to solve zeolite structures from three-dimensional electron diffraction data

The programFOCUS[Grosse-Kunstleve, McCusker & Baerlocher (1997).J. Appl. Cryst.30, 985–995] was originally developed to solve zeolite structures from X-ray powder diffraction data. It uses zeolite-specific chemical information (three-dimensional 4-connected framework structure with known bond distances and angles) to supplement the diffraction data. In this way, it is possible to compensate, at least in part, for the ambiguity of the reflection intensities resulting from reflection overlap, and the program has proven to be quite successful. Recently, advances in electron microscopy have led to the development of automated diffraction tomography (ADT) and rotation electron diffraction (R…

Rational assembly and dual functionalization of Au@MnO heteroparticles on TiO2 nanowires

Au–MnO heteroparticles were immobilized on the surface of TiO2 nanowires and tagged subsequently with a fluorescent ligand. The immobilization of the Au@MnO heteroparticles was achieved by functionalizing the TiO2 nanowire support with a polymer containing catechol anchor groups for binding to the metal oxide surface and amine groups for conjugation to the Au domains of the Au@MnO heteroparticles. The Au domain of the resulting TiO2@Au–MnO nanocomposite could be functionalized selectively with a thiol-tagged 24 mer oligomer containing Texas red (SH-ODN-TXS red), whereas a green dye (NBD–Cl) could be anchored selectively to the TiO2 “support” using the free amine groups of the polymeric liga…

Evidence of noncentrosymmetry of human tooth hydroxyapatite crystals

Herein, we investigate human single hydroxyapatite crystals (enamel and dentine) by convergent-beam electron diffraction (CBED) and automated electron-diffraction tomography (ADT). The CBED pattern shows the absence of the mirror plane perpendicular to the c axis leading to the P63 space group instead of the P63 /m space group considered for larger-scale crystals, this is confirmed by ADT. This experimental evidence is of prime importance for understanding the morphogenesis and the architectural organization of calcified tissues.

From Single Molecules to Nanoscopically Structured Materials: Self-Assembly of Metal Chalcogenide/Metal Oxide Nanostructures Based on the Degree of Pearson Hardness

A chemically specific and facile method for the immobilization of metal oxide nanoparticles onto the surface of IF-MoS2 nested fullerenes is reported. The modification strategy is based on the chalcophilic affinity of transition metals such as Fe2+/Fe3+, Fe3+, or Zn2+ as described by the Pearson HSAB concept. The binding capabilities of the 3d metals are dictated by their Pearson hardness. Pearson hard cations such as Fe3+ (Fe2O3) do not bind to the chalcogenide surfaces; borderline metals such as Fe2+ (Fe3O4) or Zn2+ (ZnO) bind reversibly. Pearson-soft metals like Au bind irreversibly. The immobilization of metal oxide nanoparticle colloids was monitored by transmission electron microscopy…

ChemInform Abstract: Solution Synthesis of a New Thermoelectric Zn1+xSb Nanophase and Its Structure Determination Using Automated Electron Diffraction Tomography.

Thermoelectric nanoparticles of the nominal composition Zn4Sb3 are prepared by heating Sb nanoparticles with a 9-fold excess of Zn particles (synthesized by reaction of SbCl3 or ZnCl2 with Li[Et3BH] in THF at room temperature, and about 65 °C, respectively) in trioctylamine at about 300 °C for 225 min.

Synthesis of Fullerene- and Nanotube-Like SnS2 Nanoparticles and Sn/S/Carbon Nanocomposites

SnS2 nested fullerene-type (IF) nanoparticles, nanotubes, and SnS2/C hybrid nanostructures were obtained by vapor transport starting from elemental tin and CS2. The reaction was carried out in a single-step process by heating elemental tin metal powder in a horizontal tube furnace at 800−1000 °C. TEM analysis allowed proposing a plausible mechanism for the formation of fullerene-like particles of SnS2 as well as tubes and scrolls from nanosheets of SnS2. Pure material could be obtained by optimizing the reaction based on a product analysis using powder X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) combined with energy-dispersive X-ray spectroscopy (EDX…

Automated diffraction tomography combined with electron precession: a new tool forab initionanostructure analysis

AbstractThree-dimensional electron diffraction data was collected with our recently developed module for automated diffraction tomography and used to solve inorganic as well as organic crystal structuresab initio. The diffraction data, which covers nearly the full relevant reciprocal space, was collected in the standard nano electron diffraction mode as well as in combination with the precession technique and was subsequently processed with a newly developed automated diffraction analysis and processing software package. Non-precessed data turned out to be sufficient forab initiostructure solution by direct methods for simple crystal structures only, while precessed data allowed structure s…

Mismatch strain versus dangling bonds: formation of "coin-roll nanowires" by stacking nanosheets.

Heusler compounds as ternary intermetallic nanoparticles: Co2FeGa

This work describes the preparation of ternary nanoparticles based on the Heusler compound Co2FeGa. Nanoparticles with sizes of about 20?nm were synthesized by reducing a methanol impregnated mixture of CoCl2 ? 6H2O, Fe(NO3)3 ? 9H2O and Ga(NO3)3 ? xH2O after loading on fumed silica. The dried samples were heated under pure H2 gas at 900??C. The obtained nanoparticles?embedded in silica?were investigated by means of x-ray diffraction (XRD), transmission electron microscopy, temperature dependent magnetometry and M??bauer spectroscopy. All methods clearly revealed the Heusler-type L21 structure of the nanoparticles. In particular, anomalous XRD data demonstrate the correct composition in addi…

IM-17: a new zeolitic material, synthesis and structure elucidation from electron diffraction ADT data and Rietveld analysis

International audience; The synthesis and the structure of IM-17, a new germanosilicate with a novel zeolitic topology, prepared hydrothermally with decamethonium as the organic structure directing agent, are reported. The structure of calcined and partially rehydrated IM-17 of chemical formula per unit cell |(H2O)14.4|[Si136.50Ge39.50O352] was solved ab initio using electron diffraction ADT data in the acentric Amm2 (setting Cm2m) space group and refined by the Rietveld method. This new zeolite framework type contains a 3D pore system made of intersecting 12, 10 and 8-ring channels.

Structure solution of zeolites by automated electron diffraction tomography - Impact and treatment of preferential orientation

Abstract In this paper the reliability of structure solution of nano-crystalline porous compounds with preferred orientation based on automated electron diffraction tomography (ADT) is discussed. It will be shown that the limitations of the data acquisition geometry can be overcome by completing the missing diffraction data with additional diffraction information. Apart from different ways of sample preparation, data merging with either additional ADT data sets or intensities derived from X-ray powder diffraction comprise an effective way to improve the accuracy of the structure solution.

Application of delta recycling to electron automated diffraction tomography data from inorganic crystalline nanovolumes

δ Recycling is a simple procedure for directly extracting phase information from Patterson-type functions [Rius (2012). Acta Cryst. A68, 399-400]. This new phasing method has a clear theoretical basis and was developed with ideal single-crystal X-ray diffraction data. On the other hand, introduction of the automated diffraction tomography (ADT) technique has represented a significant advance in electron diffraction data collection [Kolb et al. (2007). Ultramicroscopy, 107, 507-513]. When combined with precession electron diffraction, it delivers quasi-kinematical intensity data even for complex inorganic compounds, so that single-crystal diffraction data of nanometric volumes are now availa…

Essential features of the polytypic charoite-96 structure compared to charoite-90

AbstractCharoite, ideally (K,Sr,Ba,Mn)15–16(Ca,Na)32[(Si70(O,OH)180)](OH,F)4·nH20, is a rock-forming mineral from the Murun massif in Yakutia, Sakha Republic, Siberia, Russia, where it occurs in a unique alkaline intrusion. Charoite occurs as four different polytypes, which are commonly intergrown in nanocrystallme fibres. We report the structure of charoite-96(a =32.11(6),b =19.77(4),c =7.23(1) Å, β = 95.85(9)°,V =4565(24) Å3, space groupP21/m),which was solvedab initioby direct methods on the basis of 2676 unique electron diffraction reflections collected by automated diffraction tomography and refined toR1/wR2=0.34/0.37. The structure of charoite-96 is related to that of the charoite-90,…

CCDC 930933: Experimental Crystal Structure Determination

Related Article: Mark Feyand, Enrico Mugnaioli, Frederik Vermoortele, Bart Bueken, Johannes M. Dieterich, Tim Reimer, Ute Kolb, Dirk de Vos, Norbert Stock|2012|Angew.Chem.,Int.Ed.|51|10373|doi:10.1002/anie.201204963

CCDC 1429729: Experimental Crystal Structure Determination

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CCDC 1429728: Experimental Crystal Structure Determination

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