Large dynamic scissoring mode displacements coupled to band gap opening in the cubic phase of the methylammonium lead halide perovskites.

Hybrid perovskites are a rapidly growing research area, having reached photovoltaic power conversion efficiencies of over 25%. There is a increasing consensus that the structures of these materials, and hence their electronic structures, cannot be understood purely from the time and space averaged crystal structures observable by conventional methods. We apply a symmetry-motivated analysis method to analyse x-ray pair distribution function data of the cubic phases of the hybrid perovskites MAPb(= I, Br, Cl).

Targeted Synthesis of a Highly Stable Aluminium Phosphonate Metal-Organic Framework Showing Reversible HCl Adsorption.

A concept for obtaining isoreticular compounds with tri- instead of tetravalent metal cations using highly acidic reaction conditions was developed and successfully applied in a high throughput study using N,N'-piperazinebis(methylenephosphonic acid) (H PMP), that resulted in the discovery of a new porous aluminium phosphonate denoted CAU-60⋅6 HCl. The high-throughput study was subsequently extended to other trivalent metal ions. Al-CAU-60⋅6 HCl demonstrates reversible desorption of HCl (18.

Topological Transformation of Mg-Containing Layered Double Hydroxide Nanosheets for Efficient Photodriven CH Coupling.

Direct conversion of methane (CH ) to fuels and other high value-added chemicals is an attractive technology in the chemical industry; however, practical challenges to sustainable processes remain. Herein, we report the preparation of a heterostructured Co-doped MgO-based catalyst through topological transformation of a MgCo-layered double hydroxide (LDH) calcination from 200 to 1100 °C. Remarkably, the catalyst can activate CH coupling to produce C H with a selectivity of 41.

Frustrated flexibility in metal-organic frameworks.

Stimuli-responsive flexible metal-organic frameworks (MOFs) remain at the forefront of porous materials research due to their enormous potential for various technological applications. Here, we introduce the concept of frustrated flexibility in MOFs, which arises from an incompatibility of intra-framework dispersion forces with the geometrical constraints of the inorganic building units. Controlled by appropriate linker functionalization with dispersion energy donating alkoxy groups, this approach results in a series of MOFs exhibiting a new type of guest- and temperature-responsive structural flexibility characterized by reversible loss and recovery of crystalline order under full retention of framework connectivity and topology.

Unravelling Magnetic Nanochain Formation in Dispersion for In Vivo Applications.

Self-assembly of iron oxide nanoparticles (IONPs) into 1D chains is appealing, because of their biocompatibility and higher mobility compared to 2D/3D assemblies while traversing the circulatory passages and blood vessels for in vivo biomedical applications. In this work, parameters such as size, concentration, composition, and magnetic field, responsible for chain formation of IONPs in a dispersion as opposed to spatially confining substrates, are examined. In particular, the monodisperse 27 nm IONPs synthesized by an extended LaMer mechanism are shown to form chains at 4 mT, which are lengthened with applied field reaching 270 nm at 2.

Design and Precursor-based Solid-State Synthesis of Mixed-Linker Zr-MIL-140A.

Acetic acid, an alternative green solvent, was utilized for the solvothermal synthesis of four 2D materials of composition [ZrO(OAc)(BDC-F)], [ZrO(OAc)(BDC-F)], [ZrO(OAc)(BDC)], and [ZrO(OAc)(NDC)] (BDC, terephthalate; BDC-F, 2-fluoroterephthalate; BDC-F, tetrafluoroterephthalate; NDC, 2,6-naphthalenedicarboxylate). The first three compounds were subsequently reacted with terephthalic acid in solid-state reactions to form porous MIL-140A-type metal-organic frameworks and mixed-linker derivatives ([ZrO(BDC)(BDC-Y)], = 0-0.18, Y = F, F).

Influence of Thermal and Mechanical Stimuli on the Behavior of Al-CAU-13 Metal-Organic Framework.

The response of the metal-organic framework aluminum-1,4-cyclohexanedicarboxylate or Al-CAU-13 (CAU: Christian Albrecht University) to the application of thermal and mechanical stimuli was investigated using synchrotron powder X-ray diffraction (SPXRD). Variable temperature in situ SPXRD data, over the range 80-500 K, revealed a complex evolution of the structure of the water guest containing Al-CAU-13HO, the dehydration process from ca. 310 to 370 K, and also the evolution of the guest free Al-CAU-13 structure between ca.

Quasi-hydrostatic equation of state of silicon up to 1 megabar at ambient temperature.

The isothermal equation of state of silicon has been determined by synchrotron x-ray diffraction experiments up to 105.2 GPa at room temperature using diamond anvil cells. A He-pressure medium was used to minimize the effect of uniaxial stress on the sample volume and ruby, gold and tungsten pressure gauges were used.

Layered Zn[Co(CN)](CHCOO) double metal cyanide: a two-dimensional DMC phase with excellent catalytic performance.

Double metal cyanides (DMCs) are well known, industrially applied catalysts for ring opening polymerization reactions. In recent years, they have been studied for a variety of catalytic reactions, as well as other applications, such as energy storage and Cs sorption. Herein, a new, layered DMC phase (), Zn[Co(CN)](CHCOO)·4HO, was synthesized.

A Titanium(IV)-Based Metal-Organic Framework Featuring Defect-Rich Ti-O Sheets as an Oxidative Desulfurization Catalyst.

While titanium-based metal-organic frameworks (MOFs) have been widely studied for their (photo)catalytic potential, only a few Ti MOFs have been reported owing to the high reactivity of the employed titanium precursors. The synthesis of COK-47 is now presented, the first Ti carboxylate MOF based on sheets of Ti O octahedra, which can be synthesized with a range of different linkers. COK-47 can be synthesized as an inherently defective nanoparticulate material, rendering it a highly efficient catalyst for the oxidation of thiophenes.

Pressure promoted low-temperature melting of metal-organic frameworks.

Metal-organic frameworks (MOFs) are microporous materials with huge potential for chemical processes. Structural collapse at high pressure, and transitions to liquid states at high temperature, have recently been observed in the zeolitic imidazolate framework (ZIF) family of MOFs. Here, we show that simultaneous high-pressure and high-temperature conditions result in complex behaviour in ZIF-62 and ZIF-4, with distinct high- and low-density amorphous phases occurring over different regions of the pressure-temperature phase diagram.

Laser-heating system for high-pressure X-ray diffraction at the Extreme Conditions beamline I15 at Diamond Light Source.

In this article, the specification and application of the new double-sided YAG laser-heating system built on beamline I15 at Diamond Light Source are presented. This system, combined with diamond anvil cell and X-ray diffraction techniques, allows in situ and ex situ characterization of material properties at extremes of pressure and temperature. In order to demonstrate the reliability and stability of this experimental setup over a wide range of pressure and temperature, a case study was performed and the phase diagram of lead was investigated up to 80 GPa and 3300 K.

Pore closure in zeolitic imidazolate frameworks under mechanical pressure.

We investigate the pressure-dependent mechanical behaviour of the zeolitic imidazolate framework ZIF-4 (M(im); M = Co or Zn, im = imidazolate) with high pressure, synchrotron powder X-ray diffraction and mercury intrusion measurements. A displacive phase transition from a highly compressible open pore () phase with continuous porosity (space group , bulk modulus ∼1.4 GPa) to a closed pore () phase with inaccessible porosity (space group 2/, bulk modulus ∼3.

Re-Determination of the Crystal Structure of MIL-91(Al).

The structure of one of the first permanently porous metal phosphonates, MIL-91(Al) was re-determined using high resolution synchrotron powder X-ray diffraction data. The new model is in a lower symmetry space group, with no disordered ligands in the structure, whilst remaining otherwise consistent with the reported compound. New milder synthetic conditions were also developed.

Role of crystal size on swing-effect and adsorption induced structure transition of ZIF-8.

The flexibility and structure transition behaviour of ZIF-8 in a series of samples with different particle size has been studied using a combination of high-resolution N2 gas adsorption isotherms and, for the first time, a broad in situ PXRD and Rietveld analysis. During the stepped adsorption process, large particles showed a narrow adsorption/desorption pressure range with a shorter equilibrium time due to lower kinetic hindrance, deriving from higher amount of active sites. In situ PXRD showed that both the rotation of imidazole ring and a bend in the methyl group led to the gate opening of ZIF-8.

A Breathing Zirconium Metal-Organic Framework with Reversible Loss of Crystallinity by Correlated Nanodomain Formation.

The isoreticular analogue of the metal-organic framework UiO-66(Zr), synthesized with the flexible trans-1,4-cyclohexanedicarboxylic acid as linker, shows a peculiar breathing behavior by reversibly losing long-range crystalline order upon evacuation. The underlying flexibility is attributed to a concerted conformational contraction of up to two thirds of the linkers, which breaks the local lattice symmetry. X-ray scattering data are described well by a nanodomain model in which differently oriented tetragonal-type distortions propagate over about 7-10 unit cells.

Mechanical Properties of a Calcium Dietary Supplement, Calcium Fumarate Trihydrate.

The mechanical properties of calcium fumarate trihydrate, a 1D coordination polymer considered for use as a calcium source for food and beverage enrichment, have been determined via nanoindentation and high-pressure X-ray diffraction with single crystals. The nanoindentation studies reveal that the elastic modulus (16.7-33.

Mixed-linker solid solutions of functionalized pillared-layer MOFs - adjusting structural flexibility, gas sorption, and thermal responsiveness.

Flexible metal-organic frameworks (MOFs) can undergo fascinating structural transitions triggered by external stimuli, such as adsorption/desorption of specific guest molecules or temperature changes. In this detailed study we investigate the potentials and limitations of tuning framework flexibility systematically by exploiting the powerful concept of mixed-linker solid solutions. We chose the prototypical family of functionalized pillared-layer MOFs of the general type Zn2(fu(1)-bdc)2x(fu(2)-bdc)(2-2x)dabco (with x = 1.

Design of hydrophilic metal organic framework water adsorbents for heat reallocation.

A new hydrothermally stable Al polycarboxylate metal-organic framework (MOF) based on a heteroatom bio-derived aromatic spacer is designed through a template-free green synthesis process. It appears that in some test conditions this MOF outperforms the heat reallocation performances of commercial SAPO-34.

Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity.

A series of nine Ce(iv)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.

Flow-synthesis of carboxylate and phosphonate based metal-organic frameworks under non-solvothermal reaction conditions.

A continuous flow reactor was developed for the synthesis of porous metal-organic frameworks (MOFs) under mild reaction conditions. Commodity hardware was used to assemble the device, giving it a great degree of flexibility in its configuration. The use of paraffin to encapsulate reactions and also ultrasonic treatment were employed to prevent clogging of the reactor.

Data Analysis WorkbeNch (DAWN).

Synchrotron light source facilities worldwide generate terabytes of data in numerous incompatible data formats from a wide range of experiment types. The Data Analysis WorkbeNch (DAWN) was developed to address the challenge of providing a single visualization and analysis platform for data from any synchrotron experiment (including single-crystal and powder diffraction, tomography and spectroscopy), whilst also being sufficiently extensible for new specific use case analysis environments to be incorporated (e.g.

Extreme Flexibility in a Zeolitic Imidazolate Framework: Porous to Dense Phase Transition in Desolvated ZIF-4.

Desolvated zeolitic imidazolate framework ZIF-4(Zn) undergoes a discontinuous porous to dense phase transition on cooling through 140 K, with a 23 % contraction in unit cell volume. The structure of the non-porous, low temperature phase was determined from synchrotron X-ray powder diffraction data and its density was found to be slightly less than that of the densest ZIF phase, ZIF-zni. The mechanism of the phase transition involves a cooperative rotation of imidazolate linkers resulting in isotropic framework contraction and pore space minimization.

Mechanical tunability via hydrogen bonding in metal-organic frameworks with the perovskite architecture.

Two analogous metal-organic frameworks (MOFs) with the perovskite architecture, [C(NH2)3][Mn(HCOO)3] (1) and [(CH2)3NH2][Mn(HCOO)3] (2), exhibit significantly different mechanical properties. The marked difference is attributed to their distinct modes of hydrogen bonding between the A-site amine cation and the anionic framework. The stronger cross-linking hydrogen bonding in 1 gives rise to Young's moduli and hardnesses that are up to twice those in 2, while the thermal expansion is substantially smaller.