Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates†

During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed.

Low temperature synthesis of monodisperse nanoscaled ZrO2with a large specific surface area

Thermal decomposition of Zr(C(2)O(4))(2)·4H(2)O within an autoclave or in a conventional tube furnace at temperatures below 380 °C resulted in nano- and micron-sized ZrO(2), respectively. Reactions under autogenic pressure yielded monodisperse monoclinic (m) and tetragonal (t) ZrO(2) nanoparticles with an average diameter of ~8 nm and interconnected t-ZrO(2) nanoparticles with diameters of ~4 nm, depending on the synthesis temperature. Samples were characterised by X-ray diffraction (XRD), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) associated with energy dispersive X-ray spectroscopy (EDS), Raman microspectroscopy and phot…

Detecting Crystalline Nonequilibrium Phases on the Nanometer Scale

The use of Automated electron Diffraction Tomography (ADT) is presented as a novel approach for crystallization studies at the nanometer scale for nonequilibrium phases. Here, ADT was applied to elucidate the structural identity of the recently reported hexagonal morphology of caffeine crystals, which grow only on specific surfaces. Caffeine was crystallized from solution on a specially treated TEM carbon grid. The analysis of ADT data revealed that the lattice parameters of these hexagons match those of the high temperature α- form of caffeine. Furthermore, it was observed that in this hexagonal morphology, the α-form remained stable for a prolonged period of time. The stabilization of hex…

Thermally highly stable amorphous zinc phosphate intermediates during the formation of zinc phosphate hydrate.

The mechanisms by which amorphous intermediates transform into crystalline materials are still poorly understood. Here we attempt to illuminate the formation of an amorphous precursor by investigating the crystallization process of zinc phosphate hydrate. This work shows that amorphous zinc phosphate (AZP) nanoparticles precipitate from aqueous solutions prior to the crystalline hopeite phase at low concentrations and in the absence of additives at room temperature. AZP nanoparticles are thermally stable against crystallization even at 400 °C (resulting in a high temperature AZP), but they crystallize rapidly in the presence of water if the reaction is not interrupted. X-ray powder diffract…

Identification of hexanuclear Actinide(IV) carboxylates with Thorium, Uranium and Neptunium by EXAFS spectroscopy

International audience; Hydrated actinide(IV) ions undergo hydrolysis and further polymerization and precipitation with increasing pH. The resulting amorphous and partly crystalline oxydydroxides AnO(n)(OH)(4-2n)center dot xH(2)O can usually be observed as colloids above the An(IV) solubility limit. The aging process of such colloids results in crystalline AnO(2). The presence of carboxylates in the solution prevents the occurrence of such colloids by formation of polynuclear complexes through a competing reaction between hydrolysis and ligation. The majority of recently described carboxylates reveals a hexanuclear core of [An(6)(mu(3)-O)(4)(mu(3)-OH)(4)](12+) terminated by 12 carboxylate l…

Monitoring a Mechanochemical Reaction Reveals the Formation of a New ACC Defect Variant Containing the HCO 3 – Anion Encapsulated by an Amorphous Matrix

Crystal growth & design 20(10), 6831 - 6846 (2020). doi:10.1021/acs.cgd.0c00912

Insights into the In Vitro Formation of Apatite from Mg‐Stabilized Amorphous Calcium Carbonate

Exotic magnetism in the alkali sesquioxidesRb4O6andCs4O6

Among the various alkali oxides the sesquioxides ${\text{Rb}}_{4}{\text{O}}_{6}$ and ${\text{Cs}}_{4}{\text{O}}_{6}$ are of special interest. Electronic-structure calculations using the local spin-density approximation predicted that ${\text{Rb}}_{4}{\text{O}}_{6}$ should be a half-metallic ferromagnet, which was later contradicted when an experimental investigation of the temperature-dependent magnetization of ${\text{Rb}}_{4}{\text{O}}_{6}$ showed a low-temperature magnetic transition and differences between zero-field-cooled and field-cooled measurements. Such behavior is known from spin glasses and frustrated systems. ${\text{Rb}}_{4}{\text{O}}_{6}$ and ${\text{Cs}}_{4}{\text{O}}_{6}$ c…

The crystallisation of copper(ii) phenylphosphonates

The crystal structures and syntheses of four different copper(II) phenylphosphonates, the monophenylphosphonates α-, β-, and γ-Cu(O3PC6H5)·H2O (α-CuPhPmH (1) β-CuPhPmH (2) and γ-CuPhPmH (3)), and the diphosphonate Cu(HO3PC6H5)2·H2O (CuPhP2mH (4)), are presented. The compounds were synthesized from solution at room temperature, at elevated temperature, under hydrothermal conditions, and mechanochemical conditions. The structures of α-CuPhPmH (1) and CuPhP2mH (4) were solved from powder X-ray diffraction data. The structure of β-CuPhPmH (2) was solved by single crystal X-ray analysis. The structures were validated by extended X-ray absorption fine structure (EXAFS) and DTA analyses. Disorder …

Early homogenous amorphous precursor stages of calcium carbonate and subsequent crystal growth in levitated droplets.

An in situ study of the contact-free crystallization of calcium carbonate in acoustic levitated droplets is reported. The levitated droplet technique allows an in situ monitoring of the crystallization while avoiding any foreign phase boundaries that may influence the precipitation process by heterogeneous nucleation. The diffusion-controlled precipitation of CaCO3 at neutral pH starts in the initial step with the homogeneous formation of a stable, nanosized liquid-like amorphous calcium carbonate phase that undergoes in a subsequent step a solution-assisted transformation to calcite. Cryogenic scanning electron microscopy studies indicate that precipitation is not induced at the solution/a…

Divalent metal phosphonates – new aspects for syntheses, in situ characterization and structure solution

Abstract Divalent metal phosphonates are promising hybrid materials with a broad field of application. The rich coordination chemistry of the phosphonate linkers enables the formation of structures with different dimensionalities ranging from isolated complexes and layered structures to porous frameworks incorporating various functionalities through the choice of the building blocks. In brief, metal phosphonates offer an interesting opportunity for the design of multifunctional materials. Here, we provide a short review on the class of divalent metal phosphonates discussing their syntheses, structures, and applications. We present the advantages of the recently introduced mechanochemical pa…

ChemInform Abstract: Hydrate Networks under Mechanical Stress - A Case Study for Co3(PO4)2·8H2O.

The mechanochemically (ball milling) induced loss of bound H2O in Co3(PO4)2·8H2O is investigated together with an associated phase transition and its kinetics by powder synchrotron XRD and quantitative IR spectroscopy.

Magnetic properties of Co2Mn1−xFexSi Heusler alloys

Co2Mn1−xFexSi Heusler alloys with Fe concentration x = 0–0.4 as prepared by arc melting show a L21 long range order for all Fe concentrations. Magnetic properties of Co2Mn1−xFexSi Heusler alloys were investigated by magnetometry and circular magnetic dichroism. The magnetization of the Fe doped Heusler alloys is in agreement with the Slater–Pauling values expected for half-metallic ferromagnets. Element specific magnetic moments as determined by x-ray absorption using the total electron yield method are in disagreement with theoretical predictions for x = 0 but approach the predicted values as the Fe concentration increases. Surprisingly small Fe concentration increases the magnetic moments…

Ordering the amorphous – Structures in PBD LED materials

Abstract The class of 2,5 disubstituted-1,3,4-oxadiazoles containing a biphenyl unit on one side is intensively used as electron transport materials to enhance the performance of organic light emitting diodes (OLEDs). In contrast to the ongoing research on these materials insights in their structure-property relationships are still incomplete. To overcome the structural tentativeness and ambiguities the crystal structures of 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, that of the related compound 2-(4-biphenylyl)-5-phenyl-1,3,4-oxadiazole and of 2-(4-biphenylyl)-5-(2,6-dimethylphenyl)-1,3,4-oxadiazole are determined. A comparison with the results of GAUSSIAN03 calculations and…

Einfluss des Sauerstoffgehalts auf die physikalischen Eigenschaften von Sr2MO3Cl (M = Fe, Co)

Merging models of biomineralisation with concepts of nonclassical crystallisation: is a liquid amorphous precursor involved in the formation of the prismatic layer of the Mediterranean Fan Mussel Pinna nobilis?

16 pages; International audience; The calcitic prisms of Pinna nobilis (Pinnidae, Linnaeus 1758) are shown to be perfect examples of a mesocrystalline material. Based on their ultrastructure and on the occurrence of an amorphous transient precursor during the early stages of prism formation, we provide evidence for the pathway of mesocrystallisation proposed by Seto et al. (2012), which proceeds not by self-organized oriented attachment of crystalline nano-bricks but by aggregation of initially amorphous nanogranules which later transform by epitaxial nucleation to a threedimensional array of well aligned nanocrystals. We further fathom the role of a liquid amorphous calcium carbonate in bi…

Snapshots of calcium carbonate formation – a step by step analysis

Abstract Recent advances in our understanding of CaCO3 nucleation from solution have provoked new and challenging questions. We have studied CaCO3 formation using precipitation by carbonate ester hydrolysis which ensures precipitation from a strictly homogeneous solution state and allows “titrating” carbonate to a solution with a given Ca2+ concentration on a timescale suited for kinetic studies. Nucleation and crystallization were traced by combining dynamic light scattering (DLS) and transmission electron microscopy (TEM). DLS served as in situ technique to identify the nucleation time, to monitor particle size evolution, to discriminate different precipitation mechanisms and to validate …

New Insights into the Crystallization Process of Calcium Carbonate by a Contact-Free in situ Scattering Technique using a Levitating Drop Method

Hydrate Networks under Mechanical Stress – A Case Study for Co 3 (PO 4 ) 2 ·8H 2 O

The nature of the bound water in solids with hydrogen-bonded networks depends not only on temperature and pressure but also on the nature of the constituents. The collapse and reorientation of these network structures determines the stability of hydrated solids and transitions to other crystalline or amorphous phases. Here, we study the mechanochemically induced loss of bound water in Co₃(PO₄)₂·8H₂O and compare this process to the behavior under hydrostatic pressure. The associated phase transition and its kinetics were monitored by X-ray powder diffraction with Synchrotron radiation and quantitative IR spectroscopy. High shearing forces are responsible for the degradation of the hydrogen-b…

Strong stabilization of amorphous calcium carbonate emulsion by ovalbumin: gaining insight into the mechanism of 'polymer-induced liquid precursor' processes.

8 pages; International audience; The impact of the ovo proteins ovalbumin and lysozyme-present in the first stage of egg shell formation-on the homogeneous formation of the liquid amorphous calcium carbonate (LACC) precursor, was studied by a combination of complementing methods: in situ WAXS, SANS, XANES, TEM, and immunogold labeling. Lysozyme (pI = 9.3) destabilizes the LACC emulsion whereas the glycoprotein ovalbumin (pI = 4.7) extends the lifespan of the emulsified state remarkably. In the light of the presented data: (a) Ovalbumin is shown to behave commensurable to the 'polymer-induced liquid precursor' (PILP) process proposed by Gower et al. Ovalbumin can be assumed to take a key rol…

Role of Water During Crystallization of Amorphous Cobalt Phosphate Nanoparticles

The transformation of amorphous precursors into crystalline solids and the associated mechanisms are still poorly understood. We illuminate the formation and reactivity of an amorphous cobalt phosphate hydrate precursor and the role of water for its crystallization process. Amorphous cobalt phosphate hydrate nanoparticles (ACP) with diameters of ∼20 nm were prepared in the absence of additives from aqueous solutions at low concentrations and with short reaction times. To avoid the kinetically controlled transformation of metastable ACP into crystalline Co3(PO4)2 × 8 H2O (CPO) its separation must be fast. The crystallinity of ACP could be controlled through the temperature during precipitati…

CCDC 1490687: Experimental Crystal Structure Determination

Related Article: Manuel Wilke, Anke Kabelitz, Tatiana E. Gorelik, Ana Guilherme Buzanich, Uwe Reinholz, Ute Kolb, Klaus Rademann, Franziska Emmerling|2016|Dalton Trans.|45|17453|doi:10.1039/C6DT02904C

CCDC 1490689: Experimental Crystal Structure Determination

Related Article: Manuel Wilke, Anke Kabelitz, Tatiana E. Gorelik, Ana Guilherme Buzanich, Uwe Reinholz, Ute Kolb, Klaus Rademann, Franziska Emmerling|2016|Dalton Trans.|45|17453|doi:10.1039/C6DT02904C

CCDC 1490688: Experimental Crystal Structure Determination

Related Article: Manuel Wilke, Anke Kabelitz, Tatiana E. Gorelik, Ana Guilherme Buzanich, Uwe Reinholz, Ute Kolb, Klaus Rademann, Franziska Emmerling|2016|Dalton Trans.|45|17453|doi:10.1039/C6DT02904C