A pressure-amplifying framework material with negative gas adsorption transitions.

Adsorption-based phenomena are important in gas separations, such as the treatment of greenhouse-gas and toxic-gas pollutants, and in water-adsorption-based heat pumps for solar cooling systems. The ability to tune the pore size, shape and functionality of crystalline porous coordination polymers--or metal-organic frameworks (MOFs)--has made them attractive materials for such adsorption-based applications. The flexibility and guest-molecule-dependent response of MOFs give rise to unexpected and often desirable adsorption phenomena. Common to all isothermal gas adsorption phenomena, however, is increased gas uptake with increased pressure. Here we report adsorption transitions in the isotherms of a MOF (DUT-49) that exhibits a negative gas adsorption; that is, spontaneous desorption of gas (methane and n-butane) occurs during pressure increase in a defined temperature and pressure range. A combination of in situ powder X-ray diffraction, gas adsorption experiments and simulations shows that this adsorption behaviour is controlled by a sudden hysteretic structural deformation and pore contraction of the MOF, which releases guest molecules. These findings may enable technologies using frameworks capable of negative gas adsorption for pressure amplification in micro- and macroscopic system engineering. Negative gas adsorption extends the series of counterintuitive phenomena such as negative thermal expansion and negative refractive indices and may be interpreted as an adsorptive analogue of force-amplifying negative compressibility transitions proposed for metamaterials.

The role of temperature and adsorbate on negative gas adsorption transitions of the mesoporous metal-organic framework DUT-49.

Unusual adsorption phenomena, such as breathing and negative gas adsorption (NGA), are rare and challenge our thermodynamic understanding of adsorption in deformable porous solids. In particular, NGA appears to break the rules of thermodynamics in these materials by exhibiting a spontaneous release of gas accompanying an increase in pressure. This anomaly relies on long-lived metastable states. A fundamental understanding of this process is desperately required for the discovery of new materials with this exotic property. Interestingly, NGA was initially observed upon adsorption of methane at relatively low temperature, close to the respective standard boiling point of the adsorptive, and no NGA was observed at elevated temperatures. In this contribution, we present an extensive investigation of adsorption of an array of gases at various temperatures on DUT-49, a material which features an NGA transition. Experiments, featuring a wide range of gases and vapors at temperatures ranging from 21-308 K, were used to identify for each guest a critical temperature range in which NGA can be detected. The experimental results were complemented by molecular simulations that help to rationalize the absence of NGA at elevated temperatures, and the non-monotonic behavior present upon temperature decrease. Furthermore, this in-depth analysis highlights the crucial thermodynamic and kinetic conditions for NGA, which are unique to each guest and potentially other solids with similar effects. We expect this exploration to provide detailed guidelines for experimentally discovering NGA and related "rule breaking" phenomena in novel and already known materials, and provide the conditions required for the application of this effect, for example as pressure amplifying materials.

Massive Pressure Amplification by Stimulated Contraction of Mesoporous Frameworks*.

Herein we demonstrate mesoporous frameworks interacting with carbon dioxide leading to stimulated structural contractions and massive out-of-equilibrium pressure amplification well beyond ambient pressure. Carbon dioxide, a non-toxic and non-flammable working medium, is promising for the development of pressure-amplifying frameworks for pneumatic technologies and safety systems. The strong interaction of the fluid with the framework even contracts DUT-46, a framework hitherto considered as non-flexible. Synchrotron-based in situ PXRD/adsorption experiments reveal the characteristic contraction pressure for DUT-49 pressure amplification in the range of 350-680 kPa. The stimulated framework contraction expels 1.1 to 2.4 mmol g-1 CO2 leading to autonomous pressure amplification in a pneumatic demonstrator system up to 428 kPa. According to system level estimations even higher theoretical pressure amplification may be achieved between 535 and 1011 kPa.

A Stimuli-Responsive Zirconium Metal-Organic Framework Based on Supermolecular Design.

A flexible, yet very stable metal-organic framework (DUT-98, Zr6 O4 (OH)4 (CPCDC)4 (H2 O)4 , CPCDC=9-(4-carboxyphenyl)-9H-carbazole-3,6-dicarboxylate) was synthesized using a rational supermolecular building block approach based on molecular modelling of metal-organic chains and subsequent virtual interlinking into a 3D MOF. Structural characterization via synchrotron single-crystal X-ray diffraction (SCXRD) revealed the one-dimensional pore architecture of DUT-98, envisioned in silico. After supercritical solvent extraction, distinctive responses towards various gases stimulated reversible structural transformations, as detected using coupled synchrotron diffraction and physisorption techniques. DUT-98 shows a surprisingly low water uptake but a high selectivity for pore opening towards specific gases and vapors (N2 , CO2 , n-butane, alcohols) at characteristic pressure resulting in multiple steps in the adsorption isotherm and hysteretic behavior upon desorption.

Lattice-site-specific spin dynamics in double perovskite Sr2CoOsO6.

Magnetic properties and spin dynamics have been studied for the structurally ordered double perovskite Sr2CoOsO6. Neutron diffraction, muon-spin relaxation, and ac-susceptibility measurements reveal two antiferromagnetic (AFM) phases on cooling from room temperature down to 2 K. In the first AFM phase, with transition temperature TN1=108 K, cobalt (3d7, S=3/2) and osmium (5d2, S=1) moments fluctuate dynamically, while their average effective moments undergo long-range order. In the second AFM phase below TN2=67 K, cobalt moments first become frozen and induce a noncollinear spin-canted AFM state, while dynamically fluctuating osmium moments are later frozen into a randomly canted state at T≈5 K. Ab initio calculations indicate that the effective exchange coupling between cobalt and osmium sites is rather weak, so that cobalt and osmium sublattices exhibit different ground states and spin dynamics, making Sr2CoOsO6 distinct from previously reported double-perovskite compounds.

HP-CsB5O8 : synthesis and characterization of an outstanding borate exhibiting the simultaneous linkage of all structural units of borates.

The new cesium pentaborate HP-CsB5 O8 is synthesized under high-pressure/high-temperature conditions of 6 GPa and 900 °C in a Walker-type multianvil apparatus. The compound crystallizes in the orthorhombic space group Pnma (Z=4) with the parameters a=789.7(1), b=961.2(1), c=836.3(1) pm, V=0.6348(1) nm(3) , R1 =0.0359 and wR2 =0.0440 (all data). The new structure type of HP-CsB5 O8 exhibits the simultaneous linkage of trigonal BO3 groups, corner-sharing BO4 tetrahedra, and edge-sharing BO4 tetrahedra including the presence of threefold-coordinated oxygen atoms. With respect to the rich structural chemistry of borates, HP-CsB5 O8 is the second structure type possessing this outstanding combination of the main structural units of borates in one compound. The structure consists of corrugated chains of corner- and edge-sharing BO4 tetrahedra interconnected through BO3 groups forming octagonal channels. Inside these channels, cesium is 13+3-fold coordinated by oxygen atoms. (11) B MQMAS NMR spectra are analyzed to estimate the isotropic chemical shift values and quadrupolar parameters. IR and Raman spectra are obtained and compared to the calculated vibrational frequencies at the Γ-point. The high-temperature behavior is examined by means of temperature-programmed powder diffraction.

In situ observation of gating phenomena in the flexible porous coordination polymer Zn2(BPnDC)2(bpy) (SNU-9) in a combined diffraction and gas adsorption experiment.

The intrinsic structural dynamic during the adsorption of CO2 at 195 K and N2 at 77 K on flexible porous coordination polymer Zn2(BPnDC)2(bpy) (SNU-9) was studied in situ by powder XRD. The crystal structures of as made and solvent free (activated) phases were determined by single crystal X-ray diffraction. During the structural transformation caused by activation, the rearrangement of Zn-O bonds occurs that leads to changes in coordination environment of Zn atoms. Such changes lead to the contraction of the unit cell and to decreasing unit cell volume of nearly 28% in comparison to the pristine as made structure. The solvent accessible volume of the unit cell decreases from 40.8% to 12.8%. The adsorption of CO2 and N2 on SNU-9 proceeds in a different way: the formation of intermediate phase during the CO2 adsorption could be postulated, while the transformation from narrow pore form to the open structure occurs in quasi-one-step in the case of N2 adsorption (the intermediate phase is formed only in very narrow pressure region). The transformation of the structure is guest dependent and the differences in the structures of CO2@SNU-9 at 195 K and N2@SNU-9 at 77 K were proven by Pawley and Rietveld refinements of powder XRD patterns. The structure of N2@SNU-9 is identical to this of as synthesized phase, while the structure of CO2@SNU-9 differs slightly.

Simulating selected magnetic properties of TbxPr1-xAl2, a magnetocaloric compound.

TbxPr1-xAl2are ferrimagnetic materials exhibiting magnetocaloric effect that have gained considerable attention due to their potential use as an alternative in refrigeration, magnetic sensors and in information storage technology. Here using the mean field approach numerical simulations were conducted forx= 0.1, 0.2, 0.3, 0.4, 0.5, and 0.75, to analyze selected physical properties, such as x-ray and neutron powder diffraction, magnetization and heat capacity. The simulations successfully reproduced the experimental data providing a comprehensive characterization and improved understanding of this family of compound.

Lattice instability and competing spin structures in the double perovskite insulator Sr2FeOsO6.

The semiconductor Sr2FeOsO6, depending on temperature, adopts two types of spin structures that differ in the spin sequence of ferrimagnetic iron-osmium layers along the tetragonal c axis. Neutron powder diffraction experiments, 57Fe Mössbauer spectra, and density functional theory calculations suggest that this behavior arises because a lattice instability resulting in alternating iron-osmium distances fine-tunes the balance of competing exchange interactions. Thus, Sr2FeOsO6 is an example of a double perovskite, in which the electronic phases are controlled by the interplay of spin, orbital, and lattice degrees of freedom.

Cooperative light-induced breathing of soft porous crystals via azobenzene buckling.

Although light is a prominent stimulus for smart materials, the application of photoswitches as light-responsive triggers for phase transitions of porous materials remains poorly explored. Here we incorporate an azobenzene photoswitch in the backbone of a metal-organic framework producing light-induced structural contraction of the porous network in parallel to gas adsorption. Light-stimulation enables non-invasive spatiotemporal control over the mechanical properties of the framework, which ultimately leads to pore contraction and subsequent guest release via negative gas adsorption. The complex mechanism of light-gated breathing is established by a series of in situ diffraction and spectroscopic experiments, supported by quantum mechanical and molecular dynamic simulations. Unexpectedly, this study identifies a novel light-induced deformation mechanism of constrained azobenzene photoswitches relevant to the future design of light-responsive materials.

A tale of two polymorphic pharmaceuticals: pyrithyldione and propyphenazone and their 1937 co-crystal patent.

A co-crystal of two polymorphic active pharmaceutical ingredients (APIs), first reported and patented in 1937, has been prepared and thoroughly characterised, including crystal structure analysis. The existence of four crystal forms of one of the APIs, the sedative and hypnotic active pharmaceutical ingredient 3,3-diethyl-2,4(1H,3H)-pyridinedione, pyrithyldione (PYR), and of three crystal forms of the co-crystal-forming second API, the non-steroidal anti-inflammatory drug 1,2-dihydro-1,5-dimethyl-4-(1-methylethyl)-2-phenyl-3H-pyrazol-3-one, propyphenazone (PROP), has been reported previously, but they have only been partly characterised. For both compounds, none of the metastable forms exist at room temperature. DSC, hot-stage microscopy, X-ray diffraction and powder synchrotron X-ray diffraction were employed to characterise the polymorphic forms and to determine the crystal structures of forms I-III of PYR and forms I and II of PROP.

Pressure-amorphized cubic structure II clathrate hydrate: crystallization in slow motion.

A range of techniques has so far been employed for producing amorphous aqueous solutions. In case of aqueous tetrahydrofuran (THF) this comprises hyperquenching of liquid droplets, vapour co-deposition and pressure-induced amorphization of the crystalline cubic structure II clathrate. All of these samples are thermally labile and crystallize at temperatures above 110 K. We here outline a variant of the pressure-amorphization protocol developed by Suzuki [Phys. Rev. B, 2004, 70, 172108], which results in a highly crystallization resistant amorphous THF hydrate. The hydrate produced according to our protocol (annealing to 180 K at 1.8 GPa rather than to 150 K at 1.5 GPa) does not transform to the cubic structure II THF clathrate even at 150 K. We track the reason for this higher stability to the presence of crystalline remnants when following the Suzuki protocol, which are removed when using our protocol involving higher pressures and an annealing step. These crystalline remnants later serve as crystallization seeds lowering the thermal stability of the amorphous sample. Our protocol thus makes a purely amorphous THF hydrate available to the research community. We use powder X-ray diffraction to study the process of nucleation and slow crystal growth in the temperature range 160-200 K and find that the local cage structure and periodicity of the fully crystalline hydrate develops even at the earliest stages of crystallization, when the "clathrate crystal" has a size of about two unit cells.

Crystal and Magnetic Structure Transitions in BiMnO3+δ Ceramics Driven by Cation Vacancies and Temperature.

The crystal structure of BiMnO3+δ ceramics has been studied as a function of nominal oxygen excess and temperature using synchrotron and neutron powder diffraction, magnetometry and differential scanning calorimetry. Increase in oxygen excess leads to the structural transformations from the monoclinic structure (C2/c) to another monoclinic (P21/c), and then to the orthorhombic (Pnma) structure through the two-phase regions. The sequence of the structural transformations is accompanied by a modification of the orbital ordering followed by its disruption. Modification of the orbital order leads to a rearrangement of the magnetic structure of the compounds from the long-range ferromagnetic to a mixed magnetic state with antiferromagnetic clusters coexistent in a ferromagnetic matrix followed by a frustration of the long-range magnetic order. Temperature increase causes the structural transition to the nonpolar orthorhombic phase regardless of the structural state at room temperature; the orbital order is destroyed in compounds BiMnO3+δ (δ ≤ 0.14) at temperatures above 470 °C.

Compositional and Interfacial Engineering Yield High-Performance and Stable p-i-n Perovskite Solar Cells and Mini-Modules.

Through the optimization of the perovskite precursor composition and interfaces to selective contacts, we achieved a p-i-n-type perovskite solar cell (PSC) with a 22.3% power conversion efficiency (PCE). This is a new performance record for a PSC with an absorber bandgap of 1.63 eV. We demonstrate that the high device performance originates from a synergy between (1) an improved perovskite absorber quality when introducing formamidinium chloride (FACl) as an additive in the "triple cation" Cs0.05FA0.79MA0.16PbBr0.51I2.49 (Cs-MAFA) perovskite precursor ink, (2) an increased open-circuit voltage, VOC, due to reduced recombination losses when using a lithium fluoride (LiF) interfacial buffer layer, and (3) high-quality hole-selective contacts with a self-assembled monolayer (SAM) of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) on ITO electrodes. While all devices exhibit a high performance after fabrication, as determined from current-density voltage, J-V, measurements, substantial differences in device performance become apparent when considering longer-term stability data. A reduced long-term stability of devices with the introduction of a LiF interlayer is compensated for by using FACl as an additive in the metal-halide perovskite thin-film deposition. Optimized devices maintained about 80% of the initial average PCE during maximum power point (MPP) tracking for >700 h. We scaled the optimized device architecture to larger areas and achieved fully laser patterned series-interconnected mini-modules with a PCE of 19.4% for a 2.2 cm2 active area. A robust device architecture and reproducible deposition methods are fundamental for high performance and stable large-area single junction and tandem modules based on PSCs.

Cation distribution in Cu2ZnSnSe4, Cu2FeSnS4 and Cu2ZnSiSe4 by multiple-edge anomalous diffraction.

Multiple-Edge Anomalous Diffraction (MEAD) has been applied to various quaternary sulfosalts belonging to the adamantine compound family in order to validate the distribution of copper, zinc and iron cations in the structure. Semiconductors from this group of materials are promising candidates for photovoltaic applications. Their properties strongly depend on point defects, in particular related to cation order-disorder. However, Cu+, Zn2+ and Fe2+ have very similar scattering factors and are all but indistinguishable in usual X-ray diffraction experiments. Anomalous diffraction utilizes the dependency of the atomic scattering factors f' and f'' of the energy of the radiation, especially close to the element-specific absorption edges. In the MEAD technique, individual Bragg peaks are tracked over an absorption edge. The intensity changes depending on the structure factor can be highly characteristic for Miller indices selected for a specific structural problem, but require very exact measurements. Beamline KMC-2 at synchrotron BESSY II, Berlin, has been recently upgraded for this technique. Anomalous X-ray powder diffraction and XAFS compliment the data. Application of this technique confirmed established cation distribution in Cu2ZnSnSe4 (CZTSe) and Cu2FeSnS4 (CFTS). In contrast to the literature, cation distribution in Cu2ZnSiSe4 (CZSiSe) is shown to adopt a highly ordered wurtz-kesterite structure type.

The influence of deuteration on the crystal structure of hybrid halide perovskites: a temperature-dependent neutron diffraction study of FAPbBr3.

This paper discusses the full structural solution of the hybrid perovskite formamidinium lead tribromide (FAPbBr3) and its temperature-dependent phase transitions in the range from 3 K to 300 K using neutron powder diffraction and synchrotron X-ray diffraction. Special emphasis is put on the influence of deuteration on formamidinium, its position in the unit cell and disordering in comparison to fully hydrogenated FAPbBr3. The temperature-dependent measurements show that deuteration critically influences the crystal structures, i.e. results in partially-ordered temperature-dependent structural modifications in which two symmetry-independent molecule positions with additional dislocation of the molecular centre atom and molecular angle inclinations are present.

Engineering micromechanics of soft porous crystals for negative gas adsorption.

Framework materials at the molecular level, such as metal-organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host-guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks' mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases stiffness, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons. Computational modeling shows how these modifications of the building blocks tune the activation barriers within the energy landscape of the guest-free bistable frameworks. Only frameworks with free energy barriers in the range of 800 to 1100 kJ mol-1 per unit cell, and moderate yield stress of 0.6 to 1.2 nN for single ligand buckling, exhibit adsorption-induced contraction and negative gas adsorption. Advanced experimental in situ methodologies give detailed insights into the structural transitions and the adsorption behavior. The new framework DUT-160 shows the highest magnitude of NGA ever observed for nitrogen adsorption at 77 K. Our computational and experimental analysis of the energetics and mechanical response functions of porous frameworks is an important step towards tuning activation barriers in dynamic framework materials and provides critical design principles for molecular building blocks leading to pressure amplifying materials.

The phase diagram of a mixed halide (Br, I) hybrid perovskite obtained by synchrotron X-ray diffraction.

By using synchrotron X-ray powder diffraction, the temperature dependent phase diagram of the hybrid perovskite tri-halide compounds, methyl ammonium lead iodide (MAPbI3, MA+ = CH3NH3 +) and methyl ammonium lead bromide (MAPbBr3), as well as of their solid solutions, has been established. The existence of a large miscibility gap between 0.29 ≤ x ≤ 0.92 (±0.02) for the MAPb(I1-x Br x )3 solid solution has been proven. A systematic study of the lattice parameters for the solid solution series at room temperature revealed distinct deviations from Vegard's law. Furthermore, temperature dependent measurements showed that a strong temperature dependency of lattice parameters from the composition is present for iodine rich compositions. In contrast, the bromine rich compositions show an unusually low dependency of the phase transition temperature from the degree of substitution.

Towards general network architecture design criteria for negative gas adsorption transitions in ultraporous frameworks.

Switchable metal-organic frameworks (MOFs) have been proposed for various energy-related storage and separation applications, but the mechanistic understanding of adsorption-induced switching transitions is still at an early stage. Here we report critical design criteria for negative gas adsorption (NGA), a counterintuitive feature of pressure amplifying materials, hitherto uniquely observed in a highly porous framework compound (DUT-49). These criteria are derived by analysing the physical effects of micromechanics, pore size, interpenetration, adsorption enthalpies, and the pore filling mechanism using advanced in situ X-ray and neutron diffraction, NMR spectroscopy, and calorimetric techniques parallelised to adsorption for a series of six isoreticular networks. Aided by computational modelling, we identify DUT-50 as a new pressure amplifying material featuring distinct NGA transitions upon methane and argon adsorption. In situ neutron diffraction analysis of the methane (CD4) adsorption sites at 111 K supported by grand canonical Monte Carlo simulations reveals a sudden population of the largest mesopore to be the critical filling step initiating structural contraction and NGA. In contrast, interpenetration leads to framework stiffening and specific pore volume reduction, both factors effectively suppressing NGA transitions.

Determination of the miscibility gap in the solid solutions series of methylammonium lead iodide/chloride.

Perovskites are widely known for their enormous possibility of elemental substitution, which leads to a large variety of physical properties. Hybrid perovskites such as CH3NH3PbI3 (MAPbI3) and CH3NH3PbCl3 (MAPbCl3) are perovskites with an A[XII]B[VI]X[II]3-structure, where A is an organic molecule, B is a lead(II) cation and X is a halide anion of iodine or chlorine. Whereas MAPbCl3 crystallizes in the cubic space group Pm{\overline 3}m, MAPbI3 is in the tetragonal space group I4/mcm. The substitution of I by Cl leads to an increased tolerance against humidity but is challenging or even impossible due to their large difference in ionic radii. Here, the influence of an increasing Cl content in the reaction solution on the miscibility of the solid solution members is examined systematically. Powders were synthesized by two different routes depending on the I:Cl ratio. High-resolution synchrotron X-ray data are used to establish values for the limits of the miscibility gap which are 3.1 (1.1) mol% MAPbCl3 in MAPI and 1.0 (1) mol% MAPbI3 in MAPCl. The establishment of relations between average pseudo-cubic lattice parameters for both phases allows a determination of the degree of substitution from the observed lattice parameters.