Martin Etter

In Situ Monitoring and Mechanism of the Mechanochemical Formation of a Microporous MOF-74 Framework

Mechanochemistry provides a rapid, efficient route to metal-organic framework Zn-MOF-74 directly from a metal oxide and without bulk solvent. In situ synchrotron X-ray diffraction monitoring of the reaction course reveals two new phases and an unusual stepwise process in which a close-packed intermediate reacts to form the open framework. The reaction can be performed on a gram scale to yield a highly porous material after activation.

Acoustic Emission from Organic Martensites

In salient effects, still crystals of solids that switch between phases acquire a momentum and are autonomously propelled because of rapid release of elastic energy accrued during a latent structural transition induced by heat, light, or mechanical stimulation. When mechanical reconfiguration is induced by change of temperature in thermosalient crystals, bursts of detectable acoustic waves are generated prior to self-actuation. These observations provide compelling evidence that the thermosalient transitions in organic and organic-containing crystals are molecular analogues of the martensitic transitions in some metals, and metal alloys such as steel and shape-memory alloys. Within a broader context, these results reveal that, akin to metallic bonding, the intermolecular interactions in molecular solids are capable of gradual accrual and sudden release of a substantial amount of strain during anisotropic thermal expansion, followed by a rapid transformation of the crystal packing in a diffusionless, non-displacive transition.

The crystal structures of carbonyl iron powder – revised using in situ synchrotron XRPD

Abstract Although carbonyl iron powder (CIP) is an old material for magnetic applications (e.g. inductor cores), the structure of this material is still described controversially in literature. On the first glance a greyish powder exhibiting a spherical structure, CIP reveals on the second glance a nanoscopic crystalline sub-structure. The material itself contains carbon and nitrogen and its structure is described as an onion-type structure. However, the nature of the different shells and clarity on the nature of the involved carbidic and/or nitridic phases, be they crystalline, amorphous or solid solutions has not yet been achieved. In addition, it is known, that CIP transforms in H2-atmosphere to a “soft” grade, consisting of pure Fe. Again, chemical and microstructural knowledge on the transition from the “hard” to the “soft” CIP is lacking. This leads to the motivation of this study: 1. Unambiguously identify the nature and existence of the involved phases in the unreduced and hard carbonyl iron powder and in the reduced and soft iron powder particles 2. Characterize the phase transformations and microstructural changes of CIP during the thermic treatment in a hydrogen atmosphere. Different techniques were used to clarify the above mentioned points like in-situ synchrotron XRPD accompanied by electron microscopy techniques.

Revealing the Initial Reaction Behavior in the Continuous Synthesis of Metal–Organic Frameworks Using Real-Time Synchrotron X-ray Analysis

In recent years, continuous process technologies have attracted increasing attention, as a means of overcoming limitations in the repeatability and reproducibility of metal-organic framework (MOF) synthesis. Research in this area, however, has neglected to provide insight into the phenomenon leading to the formation of MOFs. In this work, we report the adaption of high-energy synchrotron powder X-ray diffraction analysis to a continuous ZIF-8 production process for online monitoring of the reaction behavior and crystallite formation during the first seconds of the MOF synthesis. It was confirmed that a diffusion-controlled growth mechanism was accelerated by additional radial diffusion processes in the flow reactor. Kinetic analysis revealed a rapid crystallite formation of ZIF-8, which was completed after 8 s of reaction time and which offers the potential for future process optimization.

Direct parameterization of the pressure-dependent volume by using an inverted approximate Vinet equation of state

Parametric refinement is used for the simultaneous modeling of a series of diffraction data, replacing single independent parameters with physical or empirical equations that are valid for the full sequence of data. For the parametric treatment of diffraction data at high pressure, pressure-dependent constraints can be introduced in the form of an equation of state (EoS). However, the parameterization needs inverse functions of the EoS and most of them are not analytically invertible. In order to overcome this drawback, Taylor series expansions of different orders of the Vinet EoS were calculated and analytically inverted. It is shown that the inverted third-order Vinet EoS approximation, in its volume and linearized version, is applicable to a wide range of materials under high pressure.

Temperature-dependent synchrotron X-ray diffraction, pair distribution function and susceptibility study on the layered compound CrTe3

Abstract Results of combined synchrotron X-ray diffraction and pair distribution function experiments performed on the layered compound CrTe3 provide evidence for a short range structural distortion of one of the two crystallographically independent CrTe6 octahedra. The distortion is caused by higher mobility of one crystallographically distinct Te ion, leading to an unusual large Debye Waller factor. In situ high temperature X-ray diffraction investigations show an initial crystallization of a minor amount of elemental Te followed by decomposition of CrTe3 into Cr5Te8 and Te. Additional experiments provide evidence that the Te impurity (<1%) cannot be avoided. Analyses of structural changes in the temperature range 100–754 K show a pronounced anisotropic expansion of the lattice parameters. The differing behavior of the crystal axes is explained on the basis of structural distortions of the Cr4Te16 structural building units. An abrupt distortion of the structure occurs at T≈250 K, which then remains nearly constant down to 100 K. The structural distortion affects the spin exchange interactions between Cr3+ cations. A significant splitting between field-cooled (fc) and zero-field-cooled (zfc) magnetic susceptibility is observed below about 200 K. Applying a small external magnetic field results in a substantial spontaneous magnetization, reminiscent of ferro- or ferrimagnet exchange interactions below ~240 K. A Debye temperature of ~150 K was extracted from heat capacity measurements.

Na2IrIVCl6: Spin–Orbital-Induced Semiconductor Showing Hydration-Dependent Structural and Magnetic Variations

Iridium(IV) oxides have gained increased attention in recent years owing to the presence of competing spin-orbit coupling and Coulomb interactions, which facilitate the emergence of novel quantum phenomena. In contrast, the electronic structure and magnetic properties of IrIV-based molecular materials remain largely unexplored. In this paper, we take a fresh look at an old but puzzling compound, Na2IrCl6, which can be hydrated to form two stable phases with formulas Na2IrCl6·2H2O and Na2IrCl6·6H2O. Their crystal structures are well illustrated based on X-ray powder diffraction data. Magnetic studies reveal that Na2IrCl6 and Na2IrCl6·2H2O are canted antiferromagnets with ordering temperatures of 7.4 and 2.7 K, respectively, whereas Na2IrCl6·6H2O is paramagnetic down to 1.8 K. First-principle calculations on Na2IrCl6 reveal a Jeff = 1/2 ground state, and the band structures show that Na2IrCl6 is a spin-orbital-induced semiconductor with an indirect gap of about 0.18 eV.

Green and rapid mechanosynthesis of high-porosity NU- and UiO-type metal–organic frameworks

The use of a dodecanuclear zirconium acetate cluster as a precursor enables the rapid, clean mechanochemical synthesis of high-microporosity metal-organic frameworks NU-901 and UiO-67, with surface areas up to 2250 m2 g-1. Real-time X-ray diffraction monitoring reveals that mechanochemical reactions involving the conventional hexanuclear zirconium methacrylate precursor are hindered by the formation of an inert intermediate, which does not appear when using the dodecanuclear acetate cluster as a reactant.

Crystal structure determination of non-stoichiometric

A new non-stoichiometric calcium ruthenate [Ca 4− x RuO 6− x with x = 1.17(1)] was synthesized by the flux growth method and characterized by the X-ray powder diffraction. The crystal structure is isostructural to the K 4 CdCl 6 type with space group R

Ca_{4−x}RuO_{6−x}

\bar 3