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A hallmark of typical structural transformations is an increase in symmetry upon heating due to entropic favourability. However, local symmetry breaking upon warming is recently evidenced in rare crystalline phases. Termed as emphanisis, the phenomenon implores exploration of fascinating thermodynamic nuances that drive unusual structural evolutions. Here, synchrotron X-ray total scattering measurements are presented on a Ruddlesden-Popper mixed halide perovskite, Cs2PbI2Cl2, which reveal signatures of emphanisis. The genesis of symmetry lowering upon heating is traced to a lone pair-driven cooperative local structural distortion composed of thermally actuated Pb off-centring and static Cl displacement. Mapping the thermal evolution of low-lying phonon modes with inelastic neutron scattering uncovers instances of mode hardening with picosecond lifetime and an intriguing soft mode at the X-point of the Brillouin zone-features conducive to ultralow thermal transport. Together, these observations highlight the fundamental and functional implications of chemical design in engendering unconventional phenomena in crystalline materials and associated properties.
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This study reports the synthesis and crystal structure determination of a novel CrTe3 phase using various experimental and theoretical methods. The average stoichiometry and local phase separation of this quenched high-pressure phase were characterized by ex situ synchrotron powder X-ray diffraction and total scattering. Several structural models were obtained using simulated annealing, but all suffered from an imperfect Rietveld refinement, especially at higher diffraction angles. Finally, a novel stoichiometrically correct crystal structure model was proposed on the basis of electron diffraction data and refined against powder diffraction data using the Rietveld method. Scanning electron microscopy-energy-dispersive X-ray spectrometry (EDX) measurements verified the targeted 1:3 (Cr:Te) average stoichiometry for the starting compound and for the quenched high-pressure phase within experimental errors. Scanning transmission electron microscopy (STEM)-EDX was used to examine minute variations of the Cr-to-Te ratio at the nanoscale. Precession electron diffraction (PED) experiments were applied for the nanoscale structure analysis of the quenched high-pressure phase. The proposed monoclinic model from PED experiments provided an improved fit to the X-ray patterns, especially after introducing atomic anisotropic displacement parameters and partial occupancy of Cr atoms. Atomic resolution STEM and simulations were conducted to identify variations in the Cr-atom site-occupancy factor. No significant variations were observed experimentally for several zone axes. The magnetic properties of the novel CrTe3 phase were investigated through temperature- and field-dependent magnetization measurements. In order to understand these properties, auxiliary theoretical investigations have been performed by first-principles electronic structure calculations and Monte Carlo simulations. The obtained results allow the observed magnetization behavior to be interpreted as the consequence of competition between the applied magnetic field and the Cr-Cr exchange interactions, leading to a decrease of the magnetization towards T = 0â K typical for antiferromagnetic systems, as well as a field-induced enhanced magnetization around the critical temperature due to the high magnetic susceptibility in this region.
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In antiquity, Pb was a common element added in the production of large bronze artifacts, especially large statues, to impart fluidity to the casting process. As Pb does not form a solid solution with pure Cu or with the Sn-Cu alloy phases, it is normally observed in the metal matrix as globular droplets embedded within or in interstitial positions among the crystals of Sn-bronze (normally the α phase) as the last crystallizing phase during the cooling process of the Cu-Sn-Pb ternary melt. The disequilibrium Sn content of the Pb droplets has recently been suggested as a viable parameter to detect modern materials [Shilstein, Berner, Feldman, Shalev & Rosenberg (2019). STAR Sci. Tech. Archaeol. Res. 5, 29-35]. The application assumes a time-dependent process, with a timescale of hundreds of years, estimated on the basis of the diffusion coefficient of Sn in Pb over a length of a few micrometres [Oberschmidt, Kim & Gupta (1982). J. Appl. Phys. 53, 5672-5677]. Therefore, Pb inclusions in recent Sn-bronze artifacts are actually a metastable solid solution of Pb-Sn containing â¼3% atomic Sn. In contrast, in ancient artifacts, unmixing processes and diffusion of Sn from the micro- and nano-inclusions of Pb to the matrix occur, resulting in the Pb inclusions containing a substantially lower or negligible amount of Sn. The Sn content in the Pb inclusions relies on accurate measurement of the lattice parameter of the phase in the Pb-Sn solid solution, since for low Sn values it closely follows Vegard's law. Here, several new measurements on modern and ancient samples are presented and discussed in order to verify the applicability of the method to the detection of modern artwork pretending to be ancient.
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SnGe4N4O4 was synthesized at high pressure (16 and 20â GPa) and high temperature (1200 and 1500°C) in a large-volume press. Powder X-ray diffraction experiments using synchrotron radiation indicate that the derived samples are mixtures of known and unknown phases. However, the powder X-ray diffraction patterns are not sufficient for structural characterization. Transmission electron microscopy studies reveal crystals of several hundreds of nanometres in size with different chemical composition. Among them, crystals of a previously unknown phase with stoichiometry SnGe4N4O4 were detected and investigated using automated diffraction tomography (ADT), a three-dimensional electron diffraction method. Via ADT, the crystal structure could be determined from single nanocrystals in space group P63mc, exhibiting a nolanite-type structure. This was confirmed by density functional theory calculations and atomic resolution scanning transmission electron microscopy images. In one of the syntheses runs a rhombohedral 6R polytype of SnGe4N4O4 could be found together with the nolanite-type SnGe4N4O4. The structure of this polymorph was solved as well using ADT.
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We show that the non-canonical nucleobase 2,6-diaminopurine (D) spontaneously base pairs with uracil (U) in water and the solid state without the need to be attached to the ribose-phosphate backbone. Depending on the reaction conditions, D and U assemble in thermodynamically stable hydrated and anhydrated D-U base-paired cocrystals. Under UV irradiation, an aqueous solution of D-U base-pair undergoes photochemical degradation, while a pure aqueous solution of U does not. Our simulations suggest that D may trigger the U photodimerization and show that complementary base-pairing modifies the photochemical properties of nucleobases, which might have implications for prebiotic chemistry.
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For the first time, we directly measured the onset and completion temperatures of polymorphic transitions under thermo-mechanochemical conditions by simultaneous in situ synchrotron powder X-ray diffraction and temperature monitoring. We determined the thermo-mechanochemical polymorphic transition temperature in 1-adamantyl-1-diamantyl ether to be 31 °C lower than the transition temperature determined by DSC. Our findings highlight the uniqueness of thermo-mechanochemical conditions, with potential applications in polymorph screening.
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The "inâ situ electrolyte" displays a concept for electric double-layer- as well as metal-ion capacitors in which the by-products formed during carbon synthesis serve directly as electrolyte salt to minimize waste. In this work, the concept is applied for lithium- and sodium-based systems realizing EDLCs containing aqueous, "Water in Salt" (up to 1.8â V) as well as organic (2.4â V) electrolytes. Via the mechanochemical synthesis, carbon materials with surface areas up to 2000â m2 g-1 and an optimal amount of remaining by-product are designed from the renewable resource lignin. Different cation-anion combinations are enabled by further modification directly inside the pores creating imide-based salts which are tracked by synchrotron inâ situ XRD. By the addition of solvents, the EDLCs show good capacitances up to 21â F g-1 combined with excellent rate performances and stabilities. Moreover, the LiTFSI loaded carbon as positive electrode introduces a new tunable lithium alternative for the pre-lithiation of Li-ion capacitors displaying a good rate performance and cyclability.
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Controlled synthesis of phase-pure metal-organic frameworks (MOFs) is essential for their application in technological areas such as catalysis or gas sorption. Yet, knowledge of their phase formation and growth remain rather limited, particularly with respect to species such as water whose vital role in MOF synthesis is often neglected. As a consequence, synthetic protocols often lack reproducibility when multiple MOFs can form from the same metal source and linker, and phase mixtures are obtained with little or no control over their composition. In this work, the role of water in the formation of the Zr-porphyrin MOF disordered PCN-224 (dPCN-224) is investigated. Through X-ray total scattering and scanning electron microscopy, it is observed that dPCN-224 forms via a metal-organic intermediate that consists of Zr6O4(OH)4 clusters linked by tetrakis(4-carboxy-phenyl)porphyrin molecules. Importantly, water is not only essential to the formation of Zr6O4(OH)4 clusters, but it also plays a primary role in dictating the formation kinetics of dPCN-224. This multidisciplinary approach to studying the speciation of dPCN-224 provides a blueprint for how Zr-MOF synthesis protocols can be assessed and their reproducibility increased, and highlights the importance of understanding the role of water as a decisive component in Zr-MOF formation.
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A plug-flow fixed-bed cell for synchrotron powder X-ray diffraction (PXRD) and X-ray absorption fine structure (XAFS) idoneous for the study of heterogeneous catalysts at high temperature, pressure and under gas flow is designed, constructed and demonstrated. The operating conditions up to 1000°C and 50â bar are ensured by a set of mass flow controllers, pressure regulators and two infra-red lamps that constitute a robust and ultra-fast heating and cooling method. The performance of the system and cell for carbon dioxide hydrogenation reactions under specified temperatures, gas flows and pressures is demonstrated both for PXRD and XAFS at the P02.1 (PXRD) and the P64 (XAFS) beamlines of the Deutsches Elektronen-Synchrotron (DESY).
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In pursuit of accessible and interpretable methods for direct and real-time observation of mechanochemical reactions, we demonstrate a tandem spectroscopic method for monitoring of ball-milling transformations combining fluorescence emission and Raman spectroscopy, accompanied by high-level molecular and periodic density-functional theory (DFT) calculations, including periodic time-dependent (TD-DFT) modelling of solid-state fluorescence spectra. This proof-of-principle report presents this readily accessible dual-spectroscopy technique as capable of observing changes to the supramolecular structure of the model pharmaceutical system indometacin during mechanochemical polymorph transformation and cocrystallisation. The observed time-resolved in situ spectroscopic and kinetic data are supported by ex situ X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy measurements. The application of first principles (ab initio) calculations enabled the elucidation of how changes in crystalline environment, that result from mechanochemical reactions, affect vibrational and electronic excited states of molecules. The herein explored interpretation of both real-time and ex situ spectroscopic data through ab initio calculations provides an entry into developing a detailed mechanistic understanding of mechanochemical milling processes and highlights the challenges of using real-time spectroscopy.
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Complex functional materials play a crucial role in a broad range of energy-related applications and in general for materials science. Revealing the structural mechanisms is challenging due to highly correlated coexisting phases and microstructures, especially for in situ or operando investigations. Since the grain sizes influence the properties, these microstructural features further complicate investigations at synchrotrons due to the limitations of illuminated sample volumes. In this study, it is demonstrated that such complex functional materials with highly correlated coexisting phases can be investigated under in situ conditions with neutron diffraction. For large grain sizes, these experiments are valuable methods to reveal the structural mechanisms. For an example of in situ experiments on barium titanate with an applied electric field, details of the electric-field-induced phase transformation depending on grain size and frequency are revealed. The results uncover the strain mechanisms in barium titanate and elucidate the complex interplay of stresses in relation to grain sizes as well as domain-wall densities and mobilities.
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Glasses, unlike crystals, are intrinsically brittle due to the absence of microstructure-controlled toughening, creating fundamental constraints for their technological applications. Consequently, strategies for toughening glasses without compromising their other advantageous properties have been long sought after but elusive. Here we report exceptional toughening in oxide glasses via paracrystallization, using aluminosilicate glass as an example. By combining experiments and computational modelling, we demonstrate the uniform formation of crystal-like medium-range order clusters pervading the glass structure as a result of paracrystallization under high-pressure and high-temperature conditions. The paracrystalline oxide glasses display superior toughness, reaching up to 1.99 ± 0.06 MPa m1/2, surpassing any other reported bulk oxide glasses, to the best of our knowledge. We attribute this exceptional toughening to the excitation of multiple shear bands caused by a stress-induced inverse transformation from the paracrystalline to amorphous states, revealing plastic deformation characteristics. This discovery presents a potent strategy for designing highly damage-tolerant glass materials and emphasizes the substantial influence of atomic-level structural variation on the properties of oxide glasses.
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We report the experimental discovery of a new structural phase of well-known orthorhombic R 2BaCuO5 (R = Sm and Eu), exhibiting a tetragonal crystal structure with space group P4∕mbm. The high-pressure tetragonal phase is isostructural with the brown phase R 2BaCuO5 (R = La, Pr, and Nd). In this structure, the Cu ions form an isolated square planar environment, contrary to the orthorhombic phase, where the Cu ions are located in a distorted square pyramid. Magnetization and specific heat measurements reveal the long-range antiferromagnetic order of the Cu2+ and/or Sm3+ moments for the Sm-sample, with the magnetic specific heat accounting for only 35% of the magnetic entropy. Interestingly, the Eu-sample remains paramagnetic down to the lowest temperature. The high Curie-Weiss temperature of -140 K and magnetic entropy of 3% of the expected value indicates that the system is highly frustrated. We estimated the isothermal entropy change and investigated the magnetocaloric effect for Eu2BaCuO5, and the maximum entropy change detected at a field of 70 kOe at 3 K reaches 5.6 J kg-1K-1.
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The outstanding diversity of Zr-based frameworks is inherently linked to the variable coordination geometry of Zr-oxo clusters and the conformational flexibility of the linker, both of which allow for different framework topologies based on the same linker-cluster combination. In addition, intrinsic structural disorder provides a largely unexplored handle to further expand the accessibility of novel metal-organic framework (MOF) structures that can be formed. In this work, we report the concomitant synthesis of three topologically different MOFs based on the same M6O4(OH)4 clusters (M = Zr or Hf) and methane-tetrakis(p-biphenyl-carboxylate) (MTBC) linkers. Two novel structural models are presented based on single-crystal diffraction analysis, namely, cubic c-(4,12)MTBC-M6 and trigonal tr-(4,12)MTBC-M6, which comprise 12-coordinated clusters and 4-coordinated tetrahedral linkers. Notably, the cubic phase features a new architecture based on orientational cluster disorder, which is essential for its formation and has been analyzed by a combination of average structure refinements and diffuse scattering analysis from both powder and single-crystal X-ray diffraction data. The trigonal phase also features structure disorder, although involving both linkers and secondary building units. In both phases, remarkable geometrical distortion of the MTBC linkers illustrates how linker flexibility is also essential for their formation and expands the range of achievable topologies in Zr-based MOFs and its analogues.
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Utilizing direct mechanocatalytical conditions, the Sonogashira coupling was successfully performed on the surface of milling tools by using pure Pd and Pd coated steel balls. The optimization of co-catalyst forming additives led to a protocol, which generates quantitative yields under aerobic conditions for various substrates within as little as 90â minutes. Using state-of-the-art spectroscopic, diffractive, as well as in situ methods lead to the identification of a previously unknown and highly reactive complex of the co-catalyst copper. This new complex differs substantially from the known complexes in liquid phase Sonogashira couplings, proving that reaction pathways in mechanochemistry may differ from those in established synthetic procedures.
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A Zr6-based metal-organic framework (MOF), MOF-808, is investigated for the adsorptive removal of IO3- from aqueous solutions, due to its high surface area and abundance of open metal sites. The uptake kinetics, adsorption capacity and binding mode are studied, showing a maximum uptake capacity of 233 mg g-1, the highest reported by any material.
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Polyanion-type phosphate materials, such as M3 V2 (PO4 )3 (M = Li/Na/K), are promising as insertion-type negative electrodes for monovalent-ion batteries including Li/Na/K-ion batteries (lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs)) with fast charging/discharging and distinct redox peaks. However, it remains a great challenge to understand the reaction mechanism of materials upon monovalent-ion insertion. Here, triclinic Mg3 V4 (PO4 )6 /carbon composite (MgVP/C) with high thermal stability is synthesized via ball-milling and carbon-thermal reduction method and applied as a pseudocapacitive negative electrode in LIBs, SIBs, and PIBs. In operando and ex situ studies demonstrate the guest ion-dependent reaction mechanisms of MgVP/C upon monovalent-ion storage due to different sizes. MgVP/C undergoes an indirect conversion reaction to form Mg0 , V0 , and Li3 PO4 in LIBs, while in SIBs/PIBs the material only experiences a solid solution with the reduction of V3+ to V2+ . Moreover, in LIBs, MgVP/C delivers initial lithiation/delithiation capacities of 961/607 mAh g-1 (30/19 Li+ ions) for the first cycle, despite its low initial Coulombic efficiency, fast capacity decay for the first 200 cycles, and limited reversible insertion/deinsertion of 2 Na+ /K+ ions in SIBs/PIBs. This work reveals a new pseudocapacitive material and provides an advanced understanding of polyanion phosphate negative material for monovalent-ion batteries with guest ion-dependent energy storage mechanisms.
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MOF-74 is an archetypal magnetic metal-organic framework (MOF) family, with metal nodes bridged by 2,5-dioxido-1,4-benzenedicarboxylic acid (H4dobdc) and arranged into one of the simplest representations of the 1D Ising magnetic model. Recently, a novel mechano-synthetic approach opened a pathway toward a series of bimetallic multivariate (1:1) M1M2-MOF-74 materials, with the uniform distribution of metal cations in the oxometallic chains, offering a unique opportunity to investigate low-dimensional magnetism in these heterometallic MOFs. We explore here how different mechanochemical procedures affect the interaction between the metal nodes of the model system of three multivariate copper(II)/zinc(II)-MOF-74 materials, two of which were obtained through a template-controlled procedure, and the third one was obtained by recently developed mechanical MOF-alloying combined with subsequent accelerated aging. While the three Cu/Zn-MOF-74 products have almost identical powder X-ray diffraction (PXRD) diffractograms and Fourier transform infrared spectra, they differ significantly in their magnetic properties, as revealed through detailed magnetization and X-band and multifrequency high-field electron spin resonance measurements. The magnetic results of the three multivariate Cu/Zn-MOF-74s were compared to the properties of the monometallic Cu-MOF-74, which shows antiferromagnetic intrachain and weaker ferromagnetic interchain interactions. Energy-dispersive X-ray spectroscopy/scanning electron microscopy and solid-state nuclear magnetic resonance spectroscopy helped rationalize the observed differences in magnetization, and in situ synchrotron PXRD monitoring of template-controlled MOF formation revealed different reaction pathways when using the zinc or copper intermediates, involving even the fleeting occurrence of a rare MOF-74 polymorph.
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The structure of a new ZIF-8 polymorph with quartz topology (qtz) is reported. This qtz-[Zn(mIm)2] phase was obtained by mechanically amorphising crystalline ZIF-8, before heating the resultant amorphous phase to between 282 and 316 °C. The high-temperature phase structure was obtained from powder X-ray diffraction, and its thermal behaviour, CO2 gas sorption properties and dye adsorption ability were investigated.
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As the periodic atomic arrangement of a crystal is made to a disorder or glassy-amorphous system by destroying the long-range order, lattice thermal conductivity, κL, decreases, and its fundamental characteristics changes. The realization of ultralow and unusual glass-like κL in a crystalline material is challenging but crucial to many applications like thermoelectrics and thermal barrier coatings. Herein, we demonstrate an ultralow (~0.20 W/m·K at room temperature) and glass-like temperature dependence (2-400 K) of κL in a single crystal of layered halide perovskite, Cs3Bi2I6Cl3. Acoustic phonons with low cut-off frequency (20 cm-1) are responsible for the low sound velocity in Cs3Bi2I6Cl3 and make the structure elastically soft. While a strong anharmonicity originates from the low energy and localized rattling-like vibration of Cs atoms, synchrotron X-ray pair-distribution function evidence a local structural distortion in the Bi-halide octahedra and Cl vacancy. The hierarchical chemical bonding and soft vibrations from selective sublattice leading to low κL is intriguing from lattice dynamical perspective as well as have potential applications.